CN100553026C - Active material of cathode, its manufacture method and rechargeable nonaqueous electrolytic battery - Google Patents
Active material of cathode, its manufacture method and rechargeable nonaqueous electrolytic battery Download PDFInfo
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- CN100553026C CN100553026C CNB2007101421807A CN200710142180A CN100553026C CN 100553026 C CN100553026 C CN 100553026C CN B2007101421807 A CNB2007101421807 A CN B2007101421807A CN 200710142180 A CN200710142180 A CN 200710142180A CN 100553026 C CN100553026 C CN 100553026C
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- nickel
- cathode
- manganese
- coat
- active material
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- 239000011149 active material Substances 0.000 title claims abstract description 247
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 535
- 239000011572 manganese Substances 0.000 claims abstract description 450
- 239000002245 particle Substances 0.000 claims abstract description 350
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 265
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 226
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 224
- 239000002131 composite material Substances 0.000 claims abstract description 202
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 140
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 125
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 54
- 239000011733 molybdenum Substances 0.000 claims abstract description 54
- 239000010410 layer Substances 0.000 claims description 176
- 239000000203 mixture Substances 0.000 claims description 146
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 132
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 99
- 239000010949 copper Substances 0.000 claims description 98
- 229910052751 metal Inorganic materials 0.000 claims description 94
- 239000011777 magnesium Substances 0.000 claims description 89
- 239000011701 zinc Substances 0.000 claims description 88
- 239000011651 chromium Substances 0.000 claims description 82
- 239000010936 titanium Substances 0.000 claims description 82
- 150000001875 compounds Chemical class 0.000 claims description 78
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000004411 aluminium Substances 0.000 claims description 63
- 229910052782 aluminium Inorganic materials 0.000 claims description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 63
- 229910052727 yttrium Inorganic materials 0.000 claims description 57
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 229910052720 vanadium Inorganic materials 0.000 claims description 52
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 52
- 229910052802 copper Inorganic materials 0.000 claims description 49
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 47
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 45
- 229910052749 magnesium Inorganic materials 0.000 claims description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 44
- 229910052796 boron Inorganic materials 0.000 claims description 44
- 229910052742 iron Inorganic materials 0.000 claims description 44
- 229910052725 zinc Inorganic materials 0.000 claims description 44
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 42
- 229910052721 tungsten Inorganic materials 0.000 claims description 42
- 239000010937 tungsten Substances 0.000 claims description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 41
- 229910052804 chromium Inorganic materials 0.000 claims description 41
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 230000004888 barrier function Effects 0.000 claims description 39
- 239000011575 calcium Substances 0.000 claims description 37
- 229910017052 cobalt Inorganic materials 0.000 claims description 34
- 239000010941 cobalt Substances 0.000 claims description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 34
- 150000002816 nickel compounds Chemical class 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 22
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 21
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910052712 strontium Inorganic materials 0.000 claims description 17
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 description 122
- -1 alkali-metal transition metal Chemical class 0.000 description 75
- 239000002904 solvent Substances 0.000 description 70
- 239000000243 solution Substances 0.000 description 61
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 53
- 238000012545 processing Methods 0.000 description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 52
- 239000002184 metal Substances 0.000 description 50
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- 239000006185 dispersion Substances 0.000 description 39
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- 239000000956 alloy Substances 0.000 description 33
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- 239000007864 aqueous solution Substances 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 31
- 239000003153 chemical reaction reagent Substances 0.000 description 28
- 239000011230 binding agent Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002243 precursor Substances 0.000 description 24
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- 238000001354 calcination Methods 0.000 description 22
- 238000005245 sintering Methods 0.000 description 20
- 239000003513 alkali Substances 0.000 description 19
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
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- 230000008859 change Effects 0.000 description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 18
- 229910010272 inorganic material Inorganic materials 0.000 description 17
- 239000010405 anode material Substances 0.000 description 16
- 239000006258 conductive agent Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 150000002484 inorganic compounds Chemical class 0.000 description 14
- 230000006872 improvement Effects 0.000 description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
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- 239000013078 crystal Substances 0.000 description 11
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- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 11
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- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical compound [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical class CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- ZOPQVUGKTLTCMT-UHFFFAOYSA-N nickel;sulfane Chemical compound S.[Ni] ZOPQVUGKTLTCMT-UHFFFAOYSA-N 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- NASANMXFTVINAA-UHFFFAOYSA-N perchloric acid yttrium Chemical compound [Y].Cl(=O)(=O)(=O)O NASANMXFTVINAA-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- 229940105965 yttrium bromide Drugs 0.000 description 1
- 229940105970 yttrium iodide Drugs 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- LFWQXIMAKJCMJL-UHFFFAOYSA-K yttrium(3+);triiodide Chemical compound I[Y](I)I LFWQXIMAKJCMJL-UHFFFAOYSA-K 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a kind of rechargeable nonaqueous electrolytic battery that can improve active material of cathode, its manufacture method of chemical stability and use it, this secondary cell has high power capacity and good charge-discharge cycles characteristic.Negative electrode (2) has active material of cathode.This active material of cathode comprises the coat at least a portion that is formed on composite oxide particle, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and is formed at least a portion of coat and comprises the superficial layer of molybdenum Mo.
Description
The cross reference of related application
The present invention is contained in the Japanese patent application No. 2006-059725 of the Japanese patent application No. 2006-059724 that submitted on March 6th, 2006, submission on March 6th, 2006 and the related theme of submitting on March 7th, 2006 of Japanese patent application No. 2006-060689, incorporates its full content into this paper by reference.
Technical field
The present invention relates to active material of cathode, make the method and the rechargeable nonaqueous electrolytic battery of this active material of cathode; The rechargeable nonaqueous electrolytic battery that for example comprises the active material of cathode of the composite oxides that contain lithium Li and cobalt Co, the method for making this active material of cathode and use active material of cathode.
Background technology
Recently, for the demand of small size secondary cell with high power capacity along with portable unit for example video camera and notebook computer development and increase.Although use the nickel-cadmium cell of alkaline electrolyte to be used as secondary cell at present, they have low cell voltage, for example about 1.2V, and be difficult to improve their energy density.Reason is for this reason studied the lithium metal secondary batteries of using the lithium metal, and it has the lightest proportion in the Solid-state Chemistry element, for example 0.534, the maximum current capacity of per unit weight in low-down electromotive force and the metal anode material.
Yet in using the secondary cell of lithium metal as anode, dendritic lithium (skeleton) is deposited on the surface of anode when charging, and charge-discharge cycles promotes its growth.The growth deterioration of skeleton the cycle characteristics of secondary cell, and further cause such trouble: skeleton grows (placing this barrier film is used to stop negative electrode to contact with anode) by barrier film (barrier film), causes internal short-circuit thus.
In order to address this problem, for example, Japanese patent application publication number co-pending (JP-A) 62-90863 has proposed such secondary cell, wherein use material with carbon element for example coke as anode, and by deviating from and mixing alkali metal ion reignition and charging.Have been found that this secondary cell can be avoided because the anode deterioration that above-mentioned reignition and charging cause.
On the other hand, inorganic compound transition metal oxide and comprise that alkali-metal transition metal chalkogenide is considered to provide the active material of cathode of about 4V cell voltage for example.Wherein, from high voltage, stability and long-life viewpoint, lithium composite xoide for example cobalt acid lithium and lithium nickelate is a material likely.
Especially, the active material of cathode that mainly comprises cobalt acid lithium has shown high voltage, and expectation can increase energy density by the charging voltage that increases it.Yet when charging voltage increased, its cycle characteristics may deterioration.Therefore, according to the prior art, add a spot of LiMn
1/3Co
1/3Ni
1/3O
2Deng or the other material of surface-coated so that the active material of cathode modification.
But making the purpose of the above-mentioned technology of active material of cathode modification by surface-coated is to obtain to have the coating of height coating, and has proposed the several different methods that addresses this problem.For example, it is confirmed that but the method for using metal hydroxides has provided good coating, and the example of this method comprises the method for describing among the JP-A-9-265985, and wherein the step of the hydroxide by using cobalt Co and manganese Mn is administered to lithium nickelate LiNiO with cobalt Co and manganese Mn
2On the surface of particle.In addition, for example, JP-A-11-71114 discloses a kind of method, and wherein the step of the hydroxide by using non-manganese metal is administered to non-manganese metal on the surface of complex Li-Mn-oxide.
In addition, for example, except that a lot of metals, JP-A-2001-106534 has described molybdenum as the metal that is administered on the negative electrode precursor nickel hydroxide particle, is used to increase the tap density of the negative electrode that obtains.In addition, for example, learn active material of cathode by JP-A-2002-75367 with the superficial layer that comprises molybdenum and/or tungsten and lithium.
In addition, JP-A-2003-123749 has described and the oxygen uptake compound powder mixed with the composite oxides that mainly comprise lithium nickelate and has calcined the mixture that obtains obtaining active material of cathode, and enumerates vfanadium compound as this oxygen uptake compound.
Summary of the invention
Yet, if metal hydroxides is administered on the composite oxide particle, heat the particle that obtains then, the calcining between the particle is carried out easily, and particle is bonded to each other easily.As a result, when in making negative electrode, it being mixed with conductive agent, in conjunction with part and particle destroyed or break, make coat peel off thus or exposed the blemish surface of particle.Compare with the surface that forms in calcining, these blemish surfaces have very high activity, therefore, the deterioration reaction of electrolyte solution and active material of cathode take place easily.
Thereby, be desirable to provide the active material of cathode that has the chemical stability of improvement by the combination that suppresses between the particle, make the method for this active material of cathode and the rechargeable nonaqueous electrolytic battery of this active material of cathode of use, this secondary cell has high power capacity and excellent charge-discharge cycles characteristic.
According to the first embodiment of the present invention, provide a kind of active material of cathode, having comprised:
Coat, this coat are formed at least a portion of composite oxide particle and comprise and contain lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise molybdenum Mo, wherein
This composite oxide particle has average composition the by formula 1 expression.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In first embodiment of the present invention, the proportion of composing of nickel and manganese Mn is preferably in 99: 1 to 30: 70 scope in the coat.
In first embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
In first embodiment of the present invention, based on composite oxide particle, the amount of coat is preferably in 0.5wt% arrives the scope of 50wt%.
Preferably, the active material of cathode according to first invention has the average particle size particle size of 2.0 μ m to 50 μ m.
Second embodiment according to the present invention provides a kind of method of making active material of cathode, comprises the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises (one or more) hydroxide that contains nickel or nickel and manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, then molybdic acid is administered at least a portion of composite oxide particle; And
Heat the composite oxide particle that obtains after using molybdic acid, so that at least a portion of composite oxide particle, form coat and superficial layer, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and this superficial layer comprises molybdenum Mo.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In second embodiment of the present invention, preferably, by being not less than in 12 the solvent and disperseing composite oxide particle mainly comprising water and pH, then nickel compound or nickel compound and manganese Mn compound are added to wherein, form (one or more) hydroxide that contains nickel or nickel and manganese Mn.
In second embodiment of the present invention, the solvent that mainly comprises water preferably comprises lithium hydroxide.
In second embodiment of the present invention, the proportion of composing of nickel and manganese Mn is preferably in 99: 1 to 30: 70 scope in the coat.
In second embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
In second embodiment of the present invention, based on composite oxide particle, the amount of coat is preferably in 0.5wt% arrives the scope of 50wt%.
In second embodiment according to the present invention, active material of cathode preferably has the average particle size particle size of 2.0 μ m to 50 μ m.
Third embodiment according to the present invention provides a kind of rechargeable nonaqueous electrolytic battery, comprising:
Negative electrode with active material of cathode;
Anode;
Barrier film; With
Electrolyte, wherein
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise molybdenum Mo, and
This composite oxide particle has average composition the by formula 1 expression.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
According to of the present invention first to the 3rd embodiment, active material of cathode is included in the coat at least a portion of composite oxide particle, and this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Ni.Therefore, can realize high charge voltage characteristic and corresponding high-energy-density characteristic, and under the high charge voltage conditions, demonstrate good charge-discharge cycles characteristic.
In of the present invention first to the 3rd embodiment, in active material of cathode, can suppress combination between the particle by use molybdic acid to the composite oxide particle that is coated with (one or more) hydroxide that comprises nickel or nickel and manganese Mn.And, owing to can avoid in conjunction with the breaking of particle, thus can reduce because the increase of the seed activity surface area that causes of breaking and the destruction of particle, thus can make full use of the advantage of coat.
According to of the present invention first to the 3rd embodiment, can further improve the stability of active material of cathode.And, use the battery of this active material of cathode can have the discharge and the charge efficiency of high power capacity and improvement.
According to the 4th embodiment of the present invention, a kind of active material of cathode is provided, comprising:
Coat, this coat are formed at least a portion of composite oxide particle and comprise (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise yttrium Y, wherein
This composite oxide particle has average composition the by formula 1 expression.
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In the 4th embodiment of the present invention, the proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat.
In the 4th embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr.
In the 4th embodiment of the present invention, preferably, be no more than the yttrium Y of 20mol% with total amount in the oxide at least a metallic element substitution tables surface layer that is selected among magnesium Mg, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, aluminium Al, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W and the zirconium Zr.
In the 4th embodiment of the present invention, be 100 weight portions based on composite oxide particle, the amount of coat preferably 0.5 weight portion to 50 weight portions.
In the 4th embodiment of the present invention, be 100 weight portions based on the cathode activity oxide, preferably 0.1 weight portion is to 10 weight portions for the amount of superficial layer, and the amount of yttrium Y is considered to yittrium oxide Y
2O
3Weight.
Active material of cathode according to the 4th invention has the average particle size particle size of 2.0 μ m to 50 μ m.
According to the 5th embodiment of the present invention, a kind of method of making active material of cathode is provided, comprise the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises (one or more) hydroxide that contains nickel and/or manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, forms the hydroxide that comprises yttrium Y then at least a portion of composite oxide particle; And
The composite oxide particle that heating obtains after formation contains yttrium Y hydroxide, so that at least a portion of composite oxide particle, form coat and superficial layer, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn, and this superficial layer comprises yttrium Y.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In the 5th embodiment of the present invention, preferably, by being not less than in 12 the solvent and disperseing composite oxide particle mainly comprising water and pH, then nickel compound and/or manganese Mn compound are added to wherein, form (one or more) hydroxide that contains nickel and/or manganese Mn.
In the 5th embodiment of the present invention, the solvent that mainly comprises water preferably comprises lithium hydroxide.
In the 5th embodiment of the present invention, the proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat.
In the 5th embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr.
In the 5th embodiment of the present invention, preferably, be no more than the yttrium Y of 20mol% with total amount in the oxide at least a metallic element substitution tables surface layer that is selected among magnesium Mg, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, aluminium Al, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W and the zirconium Zr.
In the 5th embodiment of the present invention, be 100 weight portions based on composite oxide particle, the amount of coat preferably at 0.5 weight portion in the scope of 50 weight portions.
In the 5th embodiment of the present invention, be 100 weight portions based on active material of cathode, the amount of superficial layer preferably at 0.1 weight portion in the scope of 10 weight portions, the amount of yttrium Y is considered to yittrium oxide Y
2O
3Weight.
In the 5th embodiment of the present invention, active material of cathode preferably has the average particle size particle size of 2.0 μ m to 50 μ m.
According to the 6th embodiment of the present invention, a kind of rechargeable nonaqueous electrolytic battery is provided, comprising:
Negative electrode;
Anode;
Barrier film; With
Electrolyte, wherein
This negative electrode has active material of cathode,
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise and contain yttrium Y oxide, and
This composite oxide particle has average composition the by formula 1 expression.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
According to the of the present invention the 4th to the 6th embodiment, active material of cathode is included in the coat at least a portion of composite oxide particle, and this coat comprises the oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn.Therefore, can realize high charge voltage characteristic and corresponding high-energy-density characteristic, and under the high charge voltage conditions, demonstrate good charge-discharge cycles characteristic.
In the of the present invention the 4th to the 6th embodiment, in active material of cathode, can suppress combination between the particle by on the composite oxide particle that is coated with (one or more) hydroxide that comprises nickel and/or manganese Mn, forming the hydroxide contain yttrium Y.And, owing to can avoid in conjunction with the breaking of particle, thus can reduce because the increase of the seed activity surface area that causes of breaking and the destruction of particle, thus can make full use of the advantage of coat.
According to the of the present invention the 4th to the 6th embodiment, can further improve the chemical stability of active material of cathode.And, use the battery of this active material of cathode can have the discharge and the charge efficiency of high power capacity and improvement.
According to the 7th embodiment of the present invention, a kind of active material of cathode is provided, comprising:
Coat, this coat are formed at least a portion of composite oxide particle and comprise and contain lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise vanadium V, wherein
This composite oxide particle has average composition the by formula 1 expression.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In the 7th embodiment of invention, the proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat.
In the 7th embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
In the 7th embodiment of the present invention, based on composite oxide particle, the amount of coat is preferably in 0.5wt% arrives the scope of 50wt%.
Active material of cathode according to the 7th invention has the average particle size particle size of 2.0 μ m to 50 μ m.
According to the 8th embodiment of the present invention, a kind of method of making active material of cathode is provided, comprise the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises (one or more) hydroxide that contains nickel or nickel and manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, applies vanadic acid then at least a portion of composite oxide particle; And
The composite oxide particle that heating obtains after applying vanadic acid, so that at least a portion of composite oxides, form coat, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and the superficial layer that comprises vanadium V.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In the 8th embodiment of the present invention, preferably, by being not less than in 12 the solvent and disperseing composite oxide particle mainly comprising water and pH, then nickel compound or nickel compound and manganese Mn compound are added to wherein, form (one or more) hydroxide that contains nickel or nickel and manganese Mn.
In the 8th embodiment of the present invention, the solvent that mainly comprises water preferably comprises lithium hydroxide.
In the 8th embodiment of the present invention, the proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat.
In the 8th embodiment of the present invention, preferably, be no more than nickel and the manganese Mn of 40mol% with total amount in the oxide in the alternative coat of at least a metallic element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
In the 8th embodiment of the present invention, based on composite oxide particle, the amount of coat is preferably in 0.5wt% arrives the scope of 50wt%.
In the 8th embodiment according to the present invention, active material of cathode preferably has the average particle size particle size of 2.0 μ m to 50 μ m.
According to the 9th embodiment of the present invention, a kind of rechargeable nonaqueous electrolytic battery is provided, comprising:
Negative electrode with active material of cathode;
Anode;
Barrier film; With
Electrolyte, wherein
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise and contain lithium Li oxide and contain (one or more) oxide that applies element nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise vanadium V, and
This composite oxide particle has average composition the by formula 1 expression.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
According to the of the present invention the 7th to the 9th embodiment, active material of cathode is included in the coat at least a portion of composite oxide particle, and this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Ni.Therefore, can realize high charge voltage characteristic and corresponding high-energy-density characteristic, and under the high charge voltage conditions, demonstrate good charge-discharge cycles characteristic.
In the of the present invention the 7th to the 9th embodiment, in active material of cathode, can suppress combination between the particle by use vanadic acid to the composite oxide particle of using (one or more) hydrogen-oxygen thing that contains nickel or nickel and manganese Mn.And, owing to can avoid in conjunction with the breaking of particle, thus can reduce because the increase of the seed activity surface area that causes of breaking and the destruction of particle, thus can make full use of the advantage of coat.
According to the of the present invention the 7th to the 9th embodiment, can further improve the stability of active material of cathode.And, use the battery of this active material of cathode can have the discharge and the charge efficiency of high power capacity and improvement.
According to following description, other features and advantages of the present invention will be more obvious in conjunction with the accompanying drawings, and wherein identical Reference numeral is represented identical or similar part in whole accompanying drawings of the present invention.
Description of drawings
Fig. 1 is the schematic cross-sectional view that shows as first embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode that uses according to the present invention first, second and the 3rd embodiment;
Fig. 2 is the enlarged cross-sectional view of the part of the rolled electrode assembly shown in the displayed map 1;
Fig. 3 is the schematic diagram that shows as second embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode that uses according to the present invention first, second and the 3rd embodiment;
Fig. 4 is the amplification cross section of the part of the cell device shown in the displayed map 3;
Fig. 5 is the schematic cross-sectional view that shows as using the 3rd embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode of the the 4th, the 5th and the 6th embodiment according to the present invention;
Fig. 6 is the enlarged cross-sectional view of the part of the rolled electrode assembly shown in the displayed map 5;
Fig. 7 is the schematic diagram that shows as using the 4th embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode of the the 4th, the 5th and the 6th embodiment according to the present invention;
Fig. 8 is the amplification cross section of the part of the cell device shown in the displayed map 7;
Fig. 9 is the schematic cross-sectional view that shows as using the 5th embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode of the the 7th, the 8th and the 9th embodiment according to the present invention;
Figure 10 is the enlarged cross-sectional view of the part of the rolled electrode assembly shown in the displayed map 9;
Figure 11 is the schematic diagram that shows as using the 6th embodiment of the rechargeable nonaqueous electrolytic battery of the active material of cathode of the the 7th, the 8th and the 9th embodiment according to the present invention;
Figure 12 is the amplification cross section that shows the part of the cell device shown in Figure 11.
Embodiment
Now, will explain first, second and the 3rd embodiment of the present invention with reference to the accompanying drawings.Active material of cathode according to an embodiment of the invention has the coat at least a portion of composite oxide particle, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and have the superficial layer that comprises molybdenum Mo at least a portion of coat.
At first, will explain that active material of cathode has the reason of said structure.Mainly comprise cobalt acid lithium LiCoO
2Active material of cathode have high charge voltage characteristic and corresponding high-energy-density characteristic, but under the high power capacity of high charge voltage recharge and discharge cycles, their capacity significantly reduces.This reduction is the surface state because of active material of cathode, thereby has pointed out the surface-treated necessity of active material of cathode.
Therefore, the kinds of surface processing has been proposed.Never reduce the capacity of every volume or weight or minimize the viewpoint that capacity reduces, reduce or be coated with from the teeth outwards helping the material that the inhibition capacity reduces by the inhibition capacity, can obtain to have the active material of cathode of high charge voltage characteristic and corresponding high-energy-density characteristic and the good charge-discharge cycles characteristic under high charge voltage.
Result as inventor's further investigation, have been found that the active material of cathode that can obtain to have the good charge-discharge cycles characteristic of high power capacity under high charge voltage characteristic and corresponding high-energy-density characteristic (though they are lower slightly) and the high charge voltage conditions.By mainly comprising cobalt acid lithium LiCoO
2Active material of cathode on form contain lithium Li oxide and contain nickel and manganese Mn in the coat of (one or more) oxide of at least a coating element, obtain this active material of cathode.
Method as form cathode layer on composite oxide particle can propose following two kinds of methods.In one approach, lithium Li compound and nickel compound and/or manganese Mn compound and composite oxide particle are ground to obtain fine particle, then they are done and mix, use each other, also calcine so that form coat on the surface of composite oxide particle, this coat comprises (one or more) oxide that contains (one or more) coating element at least a among lithium Li oxide and nickeliferous N i and the manganese Mn.In another approach, lithium Li compound and nickel compound and/or manganese Mn compound be dissolved in the solvent or and solvent, and carry out wet-applying, calcining is so that form coat on the surface of this composite oxide particle then, and this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn.Yet the possibility of result that these methods obtain can't obtain the coat of high uniformity.
The inventor has also further advanced their further investigation, and has been found that (one or more) hydroxide by using nickel and/or manganese Mn and make the product dehydration that obtains form coat with the coat that generation has high uniformity by heating.Use processing according to this, dissolving nickel compound and/or manganese Mn compound in the dicyandiamide solution that mainly comprises water, in dicyandiamide solution, disperse composite oxide particle then, and add in the dispersion or the like alkali to improve this dispersion basicity, precipitation contains (one or more) hydroxide of nickel and/or manganese Mn on the surface of composite oxide particle thus.
Make the composite oxide particle dehydration of handling (one or more) hydroxide of using nickel and/or manganese Mn through using by heating, so that on composite oxide particle, form coat.Therefore, can improve the uniformity of coat on the composite oxide particle.
The inventor has further advanced their further investigation, and have been found that in following steps: (one or more) hydroxide that will contain nickel and/or manganese Mn is administered on the composite oxide particle surface, and then the particle that obtains is cleaned, dewaters and dry so that calcining, particle is bonded to each other by being applied in lip-deep (one or more) hydroxide that contains nickel and/or manganese Mn.They also find, when in conjunction with breakage of particles, because low relatively adhesion characteristics, the interface occurring between (one or more) hydroxide that contains nickel and/or manganese Mn and composite oxide particle peels off, perhaps because low adhesion strength, adhesion occurs and lost efficacy in (one or more) hydroxide that contains nickel and/or manganese Mn, this can damage the improvement of the active material of cathode characteristic of bringing by the formation coat.
In addition, the inventor also finds, if the calcination process that adds lithium Li is under situation about existing in conjunction with particle, perhaps have in its surface under the state that the particle of (one or more) hydroxide that contains nickel and/or manganese Mn contacts with each other and proceed, then the sintering between the particle is tending towards carrying out easily.
When the sintering between the particle carry out excessive the time, following problems appears.When forming negative electrode, need to increase and be used to break the input of mechanical energy of particle, carry out breakage of particles and be used for hybrid particles and binding agent and conductive agent carbon granule equably.Therefore, the active material of cathode that comprises the composite oxide particle with coat is damaged or break, cause the total number of defect particles to increase.
When the coupling part between the sintered particles is broken, formed the fracture of crack, particle, coat and peels off or the like in particle, take place to lose efficacy or fracture.Especially, with mainly comprise cobalt acid lithium LiCoO
2Active material of cathode compare, the composite oxide particle with coat tends to have a non-planar surface, rather than level and smooth surface.Because this structure, when when they apply external force, particle may be difficult to slide on each other, and on external force is easy to accumulate in a little, occurs easily thus losing efficacy or rupturing.
As a result, exposed the surface that does not form coat.In other words, exposed the surface and the active newly-generated surface that do not have coat, this does not have the surface of coat can not play the effect that improves the charge-discharge cycles characteristic.This makes the charge-discharge cycles deterioration in characteristics under the high power capacity high charge voltage conditions.The surface of exposing as is known, is active and has high surface energy.Therefore, compare with the surface that forms in the common calcining, this surface has very high activity and wash-out activity in the decomposition reaction of electrolyte solution.
In order to improve cathode function and production technology, the inventor has advanced further investigation based on the sintering between the particle.As a result, they find, when the composite oxide particle of further (one or more) hydroxide that contains nickel or nickel and manganese Mn having been used on the surface is used molybdic acid, can improve sintering process.Therefore also find, can reduce the inefficacy or the fracture of particle.Next, composite oxides, coat and superficial layer will be described.
[composite oxides]
Composite oxide particle has average composition of for example being represented by formula 1.Composite oxide particle has average composition the by formula 1 expression, therefore can have high power capacity and high discharge voltage.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In formula 1, x is in the scope of-0.10≤x≤0.10, and is preferred-0.08≤x≤0.08, and more preferably-0.06≤x≤0.06.When the value of x during less than above-mentioned scope, discharge capacity may reduce.When the value of x during greater than above-mentioned scope, lithium can diffuse out from particle, and may damage with the control of the basicity in the post-processing step, the adverse effect that when finally causing kneading (kneading) cathode paste gelation is promoted.
Y in the scope of 0≤y＜0.50, preferred 0≤y＜0.40, and more preferably 0≤y＜0.30.When the value of y during, can damage LiCoO greater than above-mentioned scope
2The high charge voltage characteristic that is had, and corresponding high-energy-density characteristic.
Z is in the scope of-0.10≤z≤0.20, and is preferred-0.08≤z≤0.18, and more preferably-0.06≤z≤0.16.When the value of z less than or during greater than above-mentioned scope, it tends to reduce discharge capacity.
Although the material that can be used as active material of cathode usually can be as the parent material of composite oxide particle, in some cases, can use by utilizing the break particle of second particle acquisition of ball mill, kneading machine or the like.
[coat]
Coat is formed at least a portion of composite oxide particle, and comprises (one or more) oxide that contains lithium Li oxide and contain (one or more) coating element of nickel or nickel and manganese Mn.The formation of this coat produces high charging voltage characteristic and corresponding high-energy-density characteristic, and can improve the charge-discharge cycles characteristic under the high power capacity high charge voltage conditions.
Preferably, coat has nickel and manganese Mn, because can obtain good charge-discharge cycles characteristic.More specifically, the proportion of composing of nickel and manganese Mn is preferably in 99: 1 to 30: 70 scope, more preferably at 99: 1 to 40: 60.Preferably, coat has the oxide of nickel and manganese Mn as oxide.This be because if the amount of manganese Mn greater than above-mentioned scope, then holding of lithium Li stays (occlusive) characteristic to reduce, and finally causes when use the reduction of the capacity of active material of cathode at that time and the increase of resistance in battery.The above-mentioned scope of the proportion of composing of nickel and manganese Mn is the scope that shows better efficient, in other words, in this scope, is added with in the process of precursor of lithium Li in calcining, has suppressed the carrying out of sintering between the particle.
Can substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
Should alternatively make and to improve the stability of active material of cathode and the diffusivity of lithium ion.The amount of selected alternative metals element is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat, preferably is no more than 30mol%, and more preferably no more than 20mol%.If the amount of selected alternative metals element is greater than above-mentioned scope, then lithium Li's holds the capacity that stays characteristic and active material of cathode and may reduce.
The amount of coat be the 0.5wt% of composite oxide particle to 50wt%, preferred 1.0wt% is to 40wt%, more preferably 2.0wt% is to 35wt%.This is because when the amount of coat during greater than above-mentioned scope, the capacity reduction of active material of cathode; Yet when the amount of coat during less than above-mentioned scope, the stability of active material of cathode reduces.
[superficial layer]
Superficial layer is formed at least a portion of coat, and comprises molybdenum Mo.The formation of superficial layer can suppress the combination between the particle.And, comprise that the superficial layer of molybdenum Mo has the effect that helps above-mentioned coat.The situation that only forms coat is compared, and superficial layer has further suppressed surperficial wash-out activity.
The average particle size particle size of active material of cathode is that 2.0 μ m are to 50 μ m.When average particle size particle size during less than 2.0 μ m, in cathode fabrication process, peel off owing to pushing, thereby and because the conductive agent that the surface area increase needs increase of active material will be added and the amount of binding agent, so it is tending towards reducing the energy density of per unit weight.On the other hand, when average particle size particle size during greater than 50 μ m, particle is tending towards passing barrier film, causes short circuit thus.
[being used to make the method for active material of cathode]
Next, will method that make active material of cathode according to an embodiment of the invention be described.The method of making active material of cathode according to an embodiment of the invention is divided into two steps: first step, on at least a portion of composite oxide particle, form the layer that comprises (one or more) hydroxide that contains nickel or nickel and manganese Mn, then molybdic acid is administered at least a portion of composite oxide particle; And second step, heat composite oxide particle after wherein using molybdic acid, so that at least a portion of composite oxide particle, form coat, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and the superficial layer that comprises molybdenum Mo.
(first step)
In a first step, contain nickel or nickel and manganese Mn (one or more) hydroxide use processing, and molybdic acid use processing.According to first step, for example, at first, composite oxide particle is dispersed in the dicyandiamide solution that mainly comprises water, dissolved the nickel compound in this dicyandiamide solution, perhaps nickel compound and manganese Mn compound.Then, join alkali in this dispersion or similar processing increases the basicity of this dispersion, precipitation contains (one or more) hydroxide of nickel or nickel and manganese Mn on the surface of composite oxide particle thus.In addition, composite oxide particle can be dispersed in the basic solvent that mainly comprises water, then can be with the nickel compound, perhaps nickel and manganese Mn compound add in this aqueous solution, and precipitation contains (one or more) hydroxide of nickel or nickel and manganese Mn thus.
The example of the parent material of nickel compound can comprise inorganic compound, for example nickel hydroxide, nickelous carbonate, nickel nitrate, nickel fluoride, nickel chloride, nickelous bromide, nickel iodide, nickelous perchlorate, bromic acid nickel, nickelous iodate, nickel oxide, nickel peroxide, nickel sulfide, nickelous sulfate, hydrogen nickel sulfide (nickel hydrogen sulfide), nickel oxide, nickelous nitrite, nickel phosphate and nickel thiocyanide; And organic compound, for example nickel oxalate and nickel acetate.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
The example of the parent material of manganese Mn can comprise inorganic compound, for example manganous hydroxide, manganese carbonate, manganese nitrate, manganous fluoride, manganese chloride, manganous bromide, manganese iodide, chloric acid manganese, perchloric acid manganese, bromic acid manganese, Manganese diiodate, manganese oxide, manganese hypophosphite, manganese sulfide, hydrogen manganese sulfide, manganese nitrate, hydrogen sulfate manganese, thiocyanic acid manganese, nitrous acid manganese, manganese phosphate, phosphate dihydrogen manganese and bicarbonate manganese; And organic compound, for example manganese oxalate and manganese acetate.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
The above-mentioned pH that mainly comprises the dicyandiamide solution of water is not less than pH 12, preferably is not less than pH 13, and more preferably is not less than pH 14.The pH of dicyandiamide solution that mainly comprises water is high more, contain nickel or nickel and manganese Mn (one or more) hydroxide to use uniformity good more, and the accuracy of reaction is high more.Therefore, owing to shortened the processing time, thus improved productivity ratio, and improved quality.Decide the pH of the dicyandiamide solution that mainly comprises water according to cost of the alkali that will use or the like.
The temperature of dispersion is not less than 40 ℃ in processing procedure, preferably is not less than 60 ℃, and more preferably is not less than 80 ℃.The temperature of dispersion is high more in the processing procedure, contain nickel or nickel and manganese Mn (one or more) hydroxide to use uniformity good more, and reaction speed is high more.Therefore, owing to shortened the processing time, thus improved productivity ratio, and improved quality.Owing to cause reduction in processing time in the improvement aspect the faster response speed, so the uniformity of using from improvement and the viewpoint of productivity ratio, can preferably use autoclave under 100 ℃, to handle, although it is to determine according to the cost of equipment and the balance between the productivity ratio.
Can regulate the pH of the dicyandiamide solution that mainly comprises water by dissolving alkali in the dicyandiamide solution that mainly comprises water.The example of alkali can comprise lithium hydroxide, NaOH, potassium hydroxide and composition thereof.Although can regulate pH,, preferably use lithium hydroxide from according to the purity of the gained active material of cathode of an embodiment and the viewpoint of performance by suitably using above-mentioned alkali.Use the advantage of lithium hydroxide as follows.Just, when the composite oxide particle that forms (one or more) hydroxide comprise nickel or nickel and manganese Mn is thereon taken out from the dicyandiamide solution that mainly comprises water, can control according to the lithium amount in the gained active material of cathode of an embodiment by the amount of application of controlling the solvent that mainly comprises water.
Subsequently, molybdic acid is administered to thereon to form comprises and contain nickel, perhaps at least a portion of the composite oxide particle of (one or more) hydroxide of nickel and manganese Mn.Under the state of particle suspending in the dicyandiamide solution that mainly comprises water of composite oxides, carry out the processing of using of molybdic acid effectively, this dicyandiamide solution that mainly comprises water be used to contain nickel or nickel and manganese Mn hydroxide use processing.By using this system, the composite oxides that are formed with the layer that comprises (one or more) hydroxide of containing nickel or nickel and manganese Mn on it are dewatered and dry step in, can suppress the combination of particle by this lip-deep (one or more) hydroxide that contains nickel or nickel and manganese Mn.
Preferably, effectively carry out the processing of using of molybdic acid in the cleaning step after using of the hydroxide that contains nickel or nickel and manganese Mn handled.Utilize this method can prevent to add to the leakage of the molybdic acid of suspension system, and improve absorption characteristic.And, use using of molybdic acid to handle and provide to promote the effect of particle aggregation, and can not cause the combination between the particle in the suspension system, and can easily clean and reclaim the particle that comes self-dispersing system.
The example of the parent material of the molybdic acid compound that can use in using processing can comprise ammonium molybdate, potassium molybdate, sodium molybdate, lithium molybdate, molybdic acid and molybdic anhydride.
Based on the weight of composite oxide particle, the amount of the molybdic acid of using is from 0.00001wt% to 1.0wt%.This amount is preferably 0.0001wt% to 0.1wt%.When the amount of the molybdic acid of using during greater than above-mentioned scope, the capacity of active material of cathode reduces.When the amount of the molybdic acid of using during less than above-mentioned scope, the stability of active material of cathode reduces.
(second step)
In second step, to separate through the composite oxide particle of using processing in first step and the dicyandiamide solution that mainly comprises water, the particle that obtains of heating is so that the dehydration of (one or more) hydroxide then, thereby on the surface of composite oxide particle, form coat, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn.Preferably in the oxidizing atmosphere that is comprising air or pure oxygen under about 300 ℃ to 1000 ℃ temperature, heat-treat.In this case, molybdic acid is attached in (one or more) hydroxide that contains nickel or nickel and manganese Mn, and this has suppressed sintering between the particle and the combination between the particle.
To separate with dicyandiamide solution through the composite oxide particle of using processing in first step, thereafter, if necessary, for the amount of regulating lithium can heat the particle that obtains subsequently with the aqueous solution impregnated granules of lithium compound.
The example of lithium compound can comprise inorganic compound, for example lithium hydroxide, lithium carbonate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, lithium iodate, lithia, lithium peroxide, lithium sulfide, hydrogen lithium sulfide, lithium sulfate, lithium hydrogen sulfate, lithium nitride, Lithium Azide, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate and lithium bicarbonate; And organic compound, for example lithium methide, ethylidene lithium, isopropyl lithium, butyl lithium, phenyl lithium, lithium oxalate and lithium acetate.
After the calcining, in case of necessity, calomel mercurous chloride is broken by using, classification or the like, can regulate particle size.
Next, will the nonaqueous electrolyte battery that use according to the active material of cathode of an embodiment of the invention described above be described.
(1) first embodiment of rechargeable nonaqueous electrolytic battery
(1-1) structure of rechargeable nonaqueous electrolytic battery
Fig. 1 has shown the cross-sectional structure that uses the rechargeable nonaqueous electrolytic battery of the active material of cathode of first embodiment according to the present invention.
Under fully charged state, this secondary cell has the open circuit voltage that for example every target and anode are not less than 4.25V and are not more than 4.65V.
This secondary cell is so-called cylindrical battery, and has rolled electrode assembly 120 in the battery case 101 of hollow cylindrical substantially.Configure volumes makes strip-shaped cathode 102 and ribbon anode 103 reel by barrier film 104 around electrode assemblie 120.
The open end of battery case 101 is connected with battery cover 107 by means of pad 110 by crimping and is formed at the relief valve device 108 and the positive temperature coefficient element (PTC element) 109 of battery cover 107 inboards.The inside of sealed cell shell 101.Battery cover 107 is by for example constituting with battery case 101 identical materials.Relief valve device 108 is electrically connected with battery cover 107 by positive temperature coefficient element 109.When because internal short-circuit or when causing the internal pressure of battery to become being not less than certain value from the heat of outside, at this moment disc 111 rollbacks (reverse) are with the electrical connection between cut-out battery cover 107 and the rolled electrode assembly 120.When temperature raise, positive temperature coefficient element 109 prevented the heat of the abnormal amount that big electric current causes thus by the resistivity Control current of increase.Pad 110 is to be made of for example surperficial insulating material that is covered with pitch.
The electrode assemblie 120 of reeling has for example center pin 112, around this center pin rolled electrode.Negative electrode 102 in the electrode assemblie 120 of reeling is connected with the cathode leg of being made by for example aluminium Al etc. 113, and anode 103 is connected with the anode tap of being made by for example nickel etc. 114.Cathode leg 113 is electrically connected with battery cover 107 by being welded to relief valve device 108, and anode tap 114 is electrically connected with battery case 101 by welding.
[negative electrode]
Fig. 2 is the guide wire of alternative shape that shows the electrode assemblie 120 of coiling shown in Figure 1.As shown in Figure 2, negative electrode 102 has the cathode mixture layer 102B on cathode current collector 102A that for example has an opposite respect to one another and the both sides that are formed on cathode current collector 102A.Cathode mixture layer 102B can be formed on cathode current collector 102A only in the zone of a side.Cathode current collector 102A is made of for example metal forming such as aluminium Al paper tinsel.Cathode mixture layer 102B comprises for example active material of cathode, and can comprise for example graphite and binding agent polyvinylidene fluoride for example of conductive agent if desired.As active material of cathode, can use active material of cathode according to above-mentioned embodiment.
[anode]
As shown in Figure 2, anode 103 has the anode collector 103A that for example has an opposite respect to one another and is formed on anode mixture layer 103B on the both sides of anode collector 103A.Anode mixture layer 103B can be formed on anode collector 103A only in the zone of a side.Anode collector 103A is made of for example metal forming such as copper Cu paper tinsel.Anode mixture layer 103B comprises for example active material of positive electrode, and can comprise for example polyvinylidene fluoride of binding agent if desired.
Active material of positive electrode comprises the anode material (hereinafter, being sometimes referred to as " anode material that can absorb/discharge lithium Li ") that can absorb and discharge lithium Li.The nitride that the example that can absorb/discharge the anode material of lithium Li can comprise material with carbon element, metallic compound, oxide, sulfide, lithium is Li N for example
3, the lithium metal, form the metal and the polymeric material of alloy with lithium.
The example of material with carbon element can comprise low graphited carbon, easy graphited carbon, graphite, RESEARCH OF PYROCARBON, coke, vitreous carbon, organic polymer compounds sintered body, carbon fiber and activated carbon.Wherein, coke can comprise pitch coke, needle coke and petroleum coke.Organic polymer compounds sintered body refer to by suitable temperature lower calcination polymeric material for example phenol plastics or furane resins make it the material that carbonization obtains, in these materials some are divided into low graphitized carbon or easy graphited carbon.The example of polymeric material can comprise polyacetylene and polypyrrole.
In can absorbing/discharge these anode materials of lithium Li, preferred charging and discharge voltage approach the charging of lithium metal and the material of discharge voltage.This is because the charging and the discharge voltage of anode 103 is low more, and battery is easy more to have higher energy density.Wherein, material with carbon element is preferred, because their crystal structure has only little variation when charging and discharge, therefore, can obtain good cycle characteristics and big charging and discharge capacity.Especially preferred graphite is because it can provide big electrochemical equivalent and high energy density.Low graphitized carbon also is preferred, because it can provide good cycle characteristics.
In addition, the anode material that can absorb/discharge lithium Li can comprise simple substance lithium metal, can form the metallic element and the semimetallic elements of alloy with lithium Li together, comprises the alloy of such element and compound or the like.These materials are preferred, because they can provide high-energy-density.Especially, more preferably they and material with carbon element are used together,, can obtain good cycle characteristics and high-energy-density because in this case.Except the alloy that comprises two kinds or more of metallic elements, alloy used herein also comprises the alloy that contains one or more metallic elements and one or more semimetallic elements.This alloy can be in following state solid solution, eutectic crystal (eutectic mixture), intermetallic compound and composition thereof.
The example of metallic element and semimetallic elements can comprise tin Sn, plumbous Pb, aluminium Al, indium In, silicon Si, zinc Zn, antimony Sb, bismuth Bi, cadmium Cd, magnesium Mg, boron, gallium Ga, germanium Ge, arsenic As, silver-colored Ag, zirconium Zr, yttrium Y and hafnium Hf.The example of above-mentioned alloy and compound can comprise having chemical formula: Ma
sMb
tLi
uMaterial and have chemical formula a: Ma
pM
qMd
rMaterial.In these chemical formulas, Ma represents and can form the metallic element of alloy and at least a element in the semimetallic elements with lithium; Mb represents metallic element except that lithium and Ma and at least a element in the semimetallic elements; Mc represents at least a element in the nonmetalloid; Md represents metallic element except that Ma and at least a element in the semimetallic elements; And s, t, u, p, q and r satisfy s＞0, t 〉=0, u 〉=0, p＞0, q＞0 and r 〉=0.
Wherein, the metallic element and the semimetallic elements of preferred IVB family short period table, and the alloy and the compound that comprise such element, and preferred especially silicon Si, tin Sn and comprise Si and/or the alloy of Sn and compound.They can be crystal or unbodied.
In addition, can in negative electrode or anode, use the inorganic compound that does not comprise lithium Li, for example MnO
2, V
2O
5, V
6O
13, NiS and MoS.
[electrolyte solution]
As electrolyte solution, can use the non-aqueous electrolytic solution that obtains by dissolving electrolytic salt in nonaqueous solvents.For example, preferred nonaqueous solvents can be for example to comprise solvent at least a in ethylene carbonate and the propylene carbonate, because they can improve cycle characteristics.Especially preferred is the mixture that comprises ethylene carbonate and propylene carbonate in electrolyte, because can further improve cycle characteristics.Nonaqueous solvents preferably includes at least a ester that is selected from the linear carbonate, and for example diethyl carbonate, dimethyl carbonate, ethylene methyl esters, and preferred carbonic acid first propyl ester are because they can further improve cycle characteristics.
Comprise 2, at least a nonaqueous solvents also is preferred in 4-difluoroanisole and the vinylene carbonate.This is that the 4-difluoroanisole can improve discharge capacity because of 2, and vinylene carbonate can improve cycle characteristics.The nonaqueous solvents that more preferably comprises its mixture is because can improve discharge capacity and cycle characteristics.
Nonaqueous solvents can also comprise following at least a compound: butylene carbonate, gamma-butyrolacton, gamma-valerolactone, its (one or more) oh group quilt (one or more) is by the compound of all or part of replacement of fluoro-containing group, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, 1, the 3-dioxolane, the 4-methyl isophthalic acid, the 3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxy-propyl nitrile, N, dinethylformamide, the N-methyl pyrrolidone, N-methyl oxazolidinone (oxazolidinone), N, N-methylimidazole alkane ketone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide (DMSO) and trimethyl phosphate.
In some cases, be included in the invertibity (refersibility) that material in the above-mentioned nonaqueous solvents can improve electrode reaction by use, according to will in conjunction with electrode, (one or more) hydroxyl of this material is replaced in whole or in part by fluorine atom.Can suitably use these materials.
Suitable example as the lithium salts of electrolytic salt can comprise LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiCl, LiBF
2(ox) difluoro lithium borate (oxalato), LiBOB and LiBr.They can use separately or can use its mixture.Wherein, LiPF
6Be preferred, because it can obtain high ionic conductivity and improve cycle characteristics.
[barrier film]
Now, will the diaphragm material that can use be described in first embodiment.As diaphragm material, can use the material that has been used for conventional batteries.In them, especially preferably use microporous polyolefin film, they have good effect to preventing short circuit, and can be by turn-offing the stability of effect improving battery.For example, the microporous barrier of preferably making by polyvinyl resin or acrylic resin.
As diaphragm material, from the viewpoint of well balanced turn-off performance and flotation property, also preferred the use has low polyacrylic duplexer or the mixture that turn-offs the polyethylene of temperature and have highly-acidproof.
(1-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, will method that make rechargeable nonaqueous electrolytic battery be described.To be that example is described this method with cylindrical rechargeable nonaqueous electrolytic battery.
Manufacturing negative electrode 102 as described below.At first, for example active material of cathode, conductive agent and binding agent are mixed with the preparation cathode mix, then the cathode mix that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of cathode mix.
Subsequently, the slurry of cathode mix is coated on the cathode current collector 102A, and dry solvent, uses roll squeezer etc. to suppress moulding then, form cathode mixture layer 102B, constitute negative electrode 102 by this cathode mixture layer.
Following manufacturing anode 103.At first, for example active material of positive electrode and binding agent are mixed with the preparation anode mixture, then the anode mixture that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of anode mixture.
Subsequently, the slurry of anode mixture is coated on the anode collector 103A, and dry solvent, uses roll squeezer etc. to suppress moulding then, form anode mixture layer 103B, constitute anode 103 by this anode mixture layer.
Next, cathode leg 113 is connected to cathode current collector 102A by for example welding, and by the welding etc. anode tap 114 is connected to anode collector 103A.Then, by barrier film 104 coiling negative electrodes 102 and anode 103, and the leading section of cathode leg 113 is welded on the relief valve device 108, the leading section with anode tap 114 is welded to battery case 101 simultaneously.Then, the negative electrode 102 and the anode 103 of reeling is clipped between a pair of insulation board 105 and 106, it is contained in the battery case 101.
Then, electrolyte solution is injected in the battery case 101, uses electrolyte solution impregnation barrier film 104 thus.Subsequently, battery cover 107, relief valve device 108 and positive temperature coefficient element 109 by the open end crimping of pad 110 at battery case 101, so that they are fixed, thereby are made rechargeable nonaqueous electrolytic battery.
(2) second of rechargeable nonaqueous electrolytic battery embodiment
(2-1) structure of rechargeable nonaqueous electrolytic battery
Fig. 3 has shown the structure of using the rechargeable nonaqueous electrolytic battery of active material of cathode according to an embodiment of the invention.As shown in Figure 3, rechargeable nonaqueous electrolytic battery has such structure, and wherein cell device 130 is contained in the clad material of being made by moistureproof stack membrane 137, and the periphery of welding cell device 130 is with sealing.Cell device 130 has cathode leg 132 and anode tap 133, and these lead-in wire encapsulated materials 137 are clipped in the middle and are drawn out to the outside.The both sides of cathode leg 132 and anode tap 133 are all covered by resin sheet 134 and resin sheet 135, so that improve the attachment characteristic to clad material 137.
[clad material]
[cell device]
Are coiling cell devices 130 by cell device shown in Figure 4 130 for example, it is stacked and reel at longitudinal direction wherein will to have ribbon anode 143, the barrier film 144 of the gel electrolyte layer 145 that is formed on its both sides, the strip-shaped cathode 142 with the gel electrolyte layer 145 that is formed on its both sides and a barrier film 144.
End at negative electrode 142 forms cathode leg 132 at longitudinal direction, and it is connected to electrode by spot welding or ultra-sonic welded.As the material of cathode leg 132, can use for example metal of aluminium.
Be similar to negative electrode 142, form anode tap 133 at an end of anode 143 at longitudinal direction, it is connected to electrode by spot welding or ultra-sonic welded.Can use the material of the metal of copper Cu for example or nickel as anode tap 133.
Because identical in parts except that gel electrolyte layer 145 and first embodiment, so below gel electrolyte layer 145 will be described.
The example of polymer compound can comprise copolymer, polytetrafluoroethylene, polyhexafluoropropylene, poly(ethylene oxide), PPOX, poly phosphazene, polysiloxanes, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, acrylonitrile-butadiene rubber, polystyrene and the Merlon of polyacrylonitrile, polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene.From the viewpoint of electrochemical stability, special optimization polypropylene nitrile, polyvinylidene fluoride, polyhexafluoropropylene and poly(ethylene oxide).
(2-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, make the method for rechargeable nonaqueous electrolytic battery with describing the active material of cathode that uses according to an embodiment of the invention.At first, with comprising the precursor solution coated cathode 142 of solvent, electrolytic salt, polymer compound and mixed solvent and each of anode 143, evaporate mixed solvent then to form gel electrolyte layer 145.By welding the end that cathode leg 132 is connected in advance cathode current collector, simultaneously, also anode tap 133 is connected to the end of anode collector 143A by welding.
Subsequently, by barrier film 144 that negative electrode 142 and anode 143 is stacked, all formed gel electrolyte layer 145 on negative electrode 142 and the anode 143, and the longitudinal direction that is stacked in that will obtain reels, to form coiling cell device 130.
Next, the clad material 137 that is made of stack membrane is drawn (drawing) to form recessed portion 136.Then, cell device 130 is incorporated in the recessed portion 136, the unprocessed portion of clad material 137 is bent to the top of recessed portion 136, the periphery that welds recessed portion 136 is then made rechargeable nonaqueous electrolytic battery thus with sealing.
[embodiment]
To describe according to embodiment of the present invention by means of embodiment, but the present invention is not limited to this.
＜embodiment 1 〉
At first, by stirring 1 hour down at 80 ℃, 20 weight portion composite oxide particles are dispersed in the pure water of 300 weight portions, this composite oxide particle has average composition Li
1.03CoO
2.01Average particle size particle size with the 13 μ m that measure by laser scattering method.
Subsequently, add the commercial reagents nitric acid nickel (NO of 1.60 weight portions to this dispersion
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 1.65 weight portions
3)
26H
2O, and in 30 minutes to wherein adding the 2N LiOH aqueous solution so that pH is adjusted to 13, and continues down to stir this dispersion at 80 ℃ and continue other 3 hours, the mixture that cooling afterwards obtains.
Next, clean this dispersion by decant, to wherein add 0.1 weight portion, be dissolved in the commercial reagents ammonium molybdate (NH in 1.0 parts by weight of purified water
4)
2MoO
4Then,, filter at last by the decant washed mixture, and at 120 ℃ of following dry filter things to form precursor.
Then, in order to regulate the amount of lithium, flood the gained precursor sample of 10 weight portions, it is mixed equably, and dry this mixture obtains the precursor that is used to calcine with the 2N LiOH aqueous solution of 2 weight portions.The temperature that flows down the precursor that the speed with 5 ℃ of per minutes will be used to calcine at air in electric furnace is elevated to 950 ℃.Kept 5 hours under this temperature, the speed with 7 ℃ of per minutes is cooled to 150 ℃ then, obtains the active material of cathode of embodiment 1.
＜embodiment 2 〉
At first, under 80 ℃, with 20 weight portions with embodiment 1 in identical composite oxide particle be dispersed in the 2N LiOH aqueous solution of 300 weight portions 2 hours (this system has 14.2 pH).Subsequently, by pure water being added to the commercial reagents nitric acid nickel (NO of 1.60 weight portions
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 1.65 weight portions
3)
26H
2The aqueous solution of preparation 10 weight portions among the O.And in 2 hours with in the dispersion that all aqueous solution of 10 weight portions of amount obtains above adding to, and continue to stir this dispersion down at 80 ℃ and continue other 1 hour, so that its cooling.
Next, clean this dispersion, the commercial reagents sodium molybdate Na in wherein adding pure water 0.2 weight portion, that be dissolved in 2.0 weight portions by decant
2MoO
4Then,, filter at last by the decant washed mixture, and at 120 ℃ of following dry filter things to form precursor.In electric furnace, flow down with the speed of 5 ℃ of per minutes the temperature of the precursor that obtains is elevated to 950 ℃ at air.Under this temperature it was kept 5 hours, the speed with 7 ℃ of per minutes is cooled to 150 ℃ then, thereby obtains the active material of cathode of embodiment 2.
＜embodiment 3 〉
Make the active material of cathode of embodiment 3 in the mode identical with embodiment 2, difference is by pure water being added to the commercial reagents nitric acid nickel (NO of 3.20 weight portions
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 3.30 weight portions
3)
26H
2The aqueous solution for preparing 20 weight portions among the O, and in 3 hours, add the aqueous solution that whole 20 weight portions of measuring obtain; And with the commercial reagents lithium molybdate Li of 0.1 weight portion
2MoO
4Be dissolved in the pure water of 1.0 weight portions, and add the aqueous solution that obtains.
＜embodiment 4 〉
Make the active material of cathode of embodiment 4 in the mode identical, be outside the difference by pure water being added to the commercial reagents nitric acid nickel (NO of 3.20 weight portions with embodiment 2
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O, 3.30 weight portions
3)
26H
2O and commercial reagents aluminum nitrate Al (NO
3)
39H
2The aqueous solution of preparation 20 weight portions among the O, and in 3 hours, add the aqueous solution that whole 20 weight portions of measuring obtain; And with the commercial reagents sodium molybdate Na of 0.1 weight portion
2MoO
4Be dissolved in the pure water of 2.0 weight portions, wherein dissolved the commercial reagents molybdic anhydride MoO of 0.05 weight portion
3, and add the aqueous solution that obtains.
＜embodiment 5 〉
Make the active material of cathode of embodiment 5 in the mode identical with embodiment 2, difference is by only add the commercial reagents nitric acid nickel (NO of 3.20 weight portions in pure water
3)
26H
2O and do not add manganese nitrate Mn (NO
3)
26H
2O prepares the aqueous solution of 20 weight portions, and adds the aqueous solution that whole 20 weight portions of measuring obtain in 3 hours; And with the commercial reagents lithium molybdate Li of 0.1 weight portion
2MoO
4Be dissolved in 1.0 parts by weight of purified water, and add this aqueous solution.
＜comparative example 1 〉
The same compound oxide particle that uses among use and the embodiment 1 is 1 active material of cathode as a comparative example, and this composite oxide particle has average composition Li
1.03CoO
2.01Average particle size particle size with the 13 μ m that measure by laser scattering method.
＜comparative example 2 〉
Remove the ammonium molybdate (NH that does not add 0.1 weight portion
4)
2MoO
4Outside make the active material of cathode of comparative example 2 in the mode identical with embodiment 1.
Measure:
Use the active material of cathode of making in embodiment 1 to 5 and comparative example 1 and 2, make the secondary cell shown in Fig. 1 and 2.At first, the prepared cathode active material powder, 10wt% of mixing 86wt% be as the graphite of conductive agent and the 4wt% polyvinylidene fluoride as binding agent, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP).Then, this dispersion is coated on the cathode current collector 102A both sides that are made of the thick banded aluminium foil of 20 μ m, and the collector drying that obtains is suppressed moulding to use roll squeezer, thereby form cathode mixture layer 102B, make negative electrode 102 thus.At this moment, thoroughly pulverize this cathode active material powder, so that pass filter screen with 70 μ m apertures with kneading machine.The porosity of cathode mixture layer 102B is controlled to be 26% volume ratio.Next, aluminium cathode leg 113 is connected to cathode current collector 102A.
Individually, 90wt% is mixed as the polyvinylidene fluoride of binding agent as the Delanium powder of active material of positive electrode and 10wt%, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-.Then, this dispersion is coated on the anode collector 103A both sides that are made of the thick banded Copper Foil of 10 μ m, and the collector drying that obtains is suppressed moulding to use roll squeezer, thereby form anode mixture layer 103B, make anode 103 thus.Next, nickel anode lead-in wire 114 is connected to anode collector 103A.
The strip-shaped cathode 102 and the ribbon anode 103 that obtain are thus much enclosed by reeling as the porous polyolefin membrane of barrier film 104, so that make the electrode assemblie 120 of screw winding.The electrode assemblie 120 of reeling is contained in the battery case 101 of irony, and a pair of insulation board 105 and 106 is placed on the top side and bottom side of rolled electrode assembly 120.Then, cathode leg 113 is guided to cathode current collector 102A outside, and be welded to relief valve device 108, similarly, anode tap 114 is guided to anode collector 103A outside, and be welded to the bottom of battery case 101.Thereafter, electrolyte solution is injected into the inside of battery case 101, and carry out crimping by 110 pairs of battery cases of pad 101, with fixedly relief valve device 108, positive temperature coefficient element 109 and battery cover 107, obtain to have the column secondary battery of 18mm overall diameter and 65mm height thus.As electrolyte solution, use electrolytic salt LiPF by dissolving 1.0mol/l in the solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1)
6The solution that obtains.
The secondary cell of so making is charged under 45 ℃ of temperature and discharge, determine initial capacity and discharge capacitance thus, this initial capacity is the discharge capacity of the circulation time first time, and this discharge capacitance is the ratio of discharge capacity with the discharge capacity that circulates for the first time of the 200th circulation.
Carry out constant current charge by constant current and reach 4.40V, carry out constant voltage charge with the constant voltage of 4.40V then and reach 2.5 hours up to total charging interval and carry out charging up to cell voltage with 1000mA.Carrying out constant-current discharge by the constant current with 800mA reaches 2.75V up to cell voltage and carries out discharge.In measurement result shown in the table 1.
[table 1]
| Initial capacity (mAh) | Discharge capacitance (%) | |
| Embodiment 1 | 2420 | 85 |
| Embodiment 2 | 2430 | 88 |
| Embodiment 3 | 2450 | 89 |
| Embodiment 4 | 2420 | 90 |
| Embodiment 5 | 2440 | 83 |
| Comparative example 1 | 2440 | 34 |
| Comparative example 2 | 2450 | 81 |
As shown in table 1, should be understood that capacity that the battery of the active material of cathode that use obtains is high and ratio use the higher discharge capacitance of battery of the active material of cathode that obtains in the comparative example 1 and 2 in embodiment 1 to 5.In addition, composition for nickel in the metal oxide and manganese Mn, the result of the discharge capacitance from embodiment 3 and embodiment 5 relatively, be understandable that, metal oxide with nickel is better than the metal oxide that only has nickel with the coexistence of the metal oxide with manganese Mn, because the former has higher charge-discharge cycles characteristic.
The present invention is not limited to above-mentioned embodiment of the present invention, can make various deformation and application under the condition that does not break away from the scope of the invention.For example, its shape is restriction especially not, can use cylindrical shape type, square type, Coin shape, button type or the like.
In first embodiment, rechargeable nonaqueous electrolytic battery with electrolyte solution as electrolyte, and in second embodiment, rechargeable nonaqueous electrolytic battery with gel electrolyte as electrolyte.Yet the present invention is not limited to this.
For example, not only can use above-mentioned electrolyte, but also can use the copolymer solid electrolyte that utilizes ionic conductive polymer, the inorganic solid electrolyte of utilizing the ionic conduction inorganic material is as electrolyte.And they can use separately or conduct is used with the electrolytical mixture of another kind.The example that is used for the polymer of solid polyelectrolyte can comprise polyethers, polyester, polyphosphazene and polysiloxanes.The example of inorganic solid electrolyte can comprise ionic conductivity ceramics, ionic conduction crystal and ionic conducting glass.
In addition, for example, the electrolyte solution in the rechargeable nonaqueous electrolytic battery has no particular limits, and can use electrolyte solution of conventional non-aqueous solvent system or the like.Wherein, the preferred example of the non-aqueous electrolytic solution that comprises alkali metal salt in the secondary cell comprises propylene carbonate, ethylene carbonate, gamma-butyrolacton, N-methyl pyrrolidone, acetonitrile, N, dinethylformamide, methyl-sulfoxide, oxolane, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxy-ethane, carbonic acid two ethyls, its derivative and composition thereof.The electrolytical preferred example that comprises in the electrolyte solution comprises alkali metal, especially calcium halide, perchlorate, rhodanate, borofluoride, fluorophosphate, fluoridize arsenic, yttrium fluoride and trifluoromethyl sulfate.
Next, explain the the 4th, the 5th and the 6th embodiment of the present invention with reference to the accompanying drawings.Active material of cathode according to an embodiment of the invention has the superficial layer on the coat at least a portion of composite oxide particle and at least a portion at coat, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn, and this superficial layer comprises and contains yttrium Y oxide.
At first, will explain that active material of cathode has the reason of said structure.Mainly comprise cobalt acid lithium LiCoO
2Active material of cathode have high charge voltage characteristic and corresponding high-energy-density characteristic, but under the high power capacity of high charge voltage recharge and discharge cycles, their capacity significantly reduces.This reduction is the surface state owing to active material of cathode, thereby has pointed out the surface-treated necessity of active material of cathode.
Therefore, the kinds of surface processing has been proposed.Never reduce the capacity of every volume or weight or minimize the viewpoint that capacity reduces, reduce or be coated with from the teeth outwards helping the material that the inhibition capacity reduces by the inhibition capacity, can obtain to have the active material of cathode of high charge voltage characteristic and corresponding high-energy-density characteristic and good charge-discharge cycles characteristic.
Result as inventor's further investigation, have been found that to obtain to have high charge voltage characteristic and corresponding high-energy-density characteristic (though they are lower slightly), and the active material of cathode of the good charge-discharge cycles characteristic of high power capacity under the high charge voltage conditions.By mainly comprising cobalt acid lithium LiCoO
2Active material of cathode on form and to comprise that the coat that contains lithium Li oxide and contain (one or more) oxide of at least a coating element among nickel and the manganese Mn obtains this active material of cathode.
Method as form coat on composite oxide particle can propose following two kinds of methods.In one approach, lithium Li compound and nickel compound and/or manganese Mn compound and composite oxide particle are ground to obtain fine particle, and they do are mixed, use each other and calcine, so that form coat on the surface of composite oxide particle, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a (one or more) coating element of nickel and manganese Mn.In another approach, lithium Li compound and nickel compound and/or manganese Mn compound be dissolved in the solvent or and solvent, and carrying out wet-applying and calcining so that on the surface of composite oxide particle, form coat, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) at least a among nickel and the manganese Mn apply element.Yet the result that these methods obtain is possible to obtain the coat of high uniformity.
The inventor has also further advanced their further investigation, and finds (one or more) hydroxide by using nickel and/or manganese Mn and make the product dehydration that obtains by heating, and the coat that has high uniformity with generation forms coat.Use processing according to this, dissolving nickel compound and/or manganese Mn compound in the dicyandiamide solution that mainly comprises water, in dicyandiamide solution, disperse composite oxide particle then, and add in the dispersion or the like alkali to improve dispersion basicity, precipitation contains (one or more) hydroxide of nickel and/or manganese Mn on the surface of composite oxide particle thus.
Make through using the composite oxide particle dehydration that (one or more) hydroxide that contains nickel and/or manganese Mn is used in processing, so that on composite oxide particle, form coat by heating.This can improve the uniformity of the coat on the composite oxide particle.Yet the present invention has further advanced their further investigation, and finds that further the sintering between the particle carries out easily in the step of calcined precursors.
When the sintering between the particle carries out following problems occurring when excessive.When forming negative electrode, need to increase and be used to break the input of mechanical energy of particle, carry out this breakage of particles and be used for hybrid particles and binding agent and conductive agent carbon granule equably.Therefore, the active material of cathode that comprises the composite oxide particle with coat is damaged or break, cause the total number of defect particles to increase.
When the coupling part between sintered particles fracture, when in particle, forming crack, particle fracture, coat and peeling off or the like, take place to lose efficacy or fracture.Especially, with mainly comprise cobalt acid lithium LiCoO
2Active material of cathode compare, the composite oxide particle with coat tends to have a non-planar surface, rather than level and smooth surface.Because this structure, when when they apply external force, particle may be difficult to slide on each other, and on external force is easy to concentrate on a little, therefore occurs inefficacy easily or ruptures.
As a result, exposed the surface that does not form coat.Change alive saying, exposed the surface and the active newly-generated surface that do not have coat, this does not have the surface of coat can not play the effect that improves the charge-discharge cycles characteristic.This makes the charge-discharge cycles deterioration in characteristics under the high power capacity high charge voltage conditions.The surface of exposing as is known, is active and has high surface energy.Therefore, compare with the surface that forms in the common calcining, this surface has very high activity and wash-out activity in the decomposition reaction of electrolyte solution.
In order to improve cathode function and manufacturing process, the inventor has advanced deep research based on the sintering between the particle.As a result, they find, when the composite oxides of further (one or more) hydroxide that contains nickel and/or manganese Mn having been used on the surface are used the hydroxide that comprises Y, can improve the process of sintering.Also have been found that the inefficacy or the fracture that can reduce particle, therefore, by using the deterioration that the effect that improves cathode surface can also improve function.
Next, will composite oxides, coat and the superficial layer that form active material of cathode according to an embodiment of the invention be described.
[composite oxides]
Composite oxide particle has average composition of for example being represented by formula 1.Composite oxide particle has average composition the by formula 1 expression, and therefore has high power capacity and high discharge voltage.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In formula 1, x is in the scope of-0.10≤x≤0.10, and is preferred-0.08≤x≤0.08, and more preferably-0.06≤x≤0.06.When the value of x during less than above-mentioned scope, discharge capacity may reduce.When the value of x during greater than above-mentioned scope, lithium can diffuse out from particle, and may damage with the control of the basicity in the post-processing step, the adverse effect that when finally causing kneading cathode paste gelation is promoted.
Y in the scope of 0≤y＜0.50, preferred 0≤y＜0.40, and more preferably 0≤y＜0.30.When the value of y during, can damage LiCoO greater than above-mentioned scope
2The high charge voltage characteristic that is had, and corresponding high-energy-density characteristic.
Z is in the scope of-0.10≤z≤0.20, and is preferred-0.08≤z≤0.18, and more preferably-0.06≤z≤0.16.When the value of z less than or during greater than above-mentioned scope, it trends towards reducing discharge capacity.
Can be although can be used as the material of active material of cathode as the parent material of composite oxide particle, in some cases, can use by utilizing the break particle of second particle acquisition of ball mill, kneading machine or the like.
[coat]
Coat is formed at least a portion of composite oxide particle, and comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn.The formation of this coat produces high charge voltage characteristic and corresponding high-energy-density characteristic, and can improve the charge-discharge cycles characteristic under high power capacity high charge voltage conditions.
The proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat, more preferably 100: 0 to 40: 60.Along with the increase of manganese Mn amount, holding of lithium Li stays characteristic to reduce, and finally causes when use the reduction of the capacity of active material of cathode at that time and the increase of resistance in battery.The above-mentioned scope of the proportion of composing of nickel and manganese Mn is the scope that shows better efficient, in other words, in this scope, is added with in the process of precursor of lithium Li in calcining, has suppressed the carrying out of the sintering between the particle.
Can substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr.
Should make for shape and can improve the stability of active material of cathode and the diffusivity of lithium ion.The amount of selected alternative metals element is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat, preferably is no more than 30mol%, and more preferably no more than 20mol%.If the amount of selected alternative metals element is greater than above-mentioned scope, then lithium Li's holds the capacity that stays characteristic and active material of cathode and may reduce.
The amount of coat be the 0.5wt% of composite oxide particle to 50wt%, preferred 1.0wt% is to 40wt%, more preferably 2.0wt% is to 35wt%.This is because when the amount of coat during greater than above-mentioned scope, the capacity reduction of active material of cathode; Yet when the amount of coat during less than above-mentioned scope, the stability of active material of cathode reduces.
[superficial layer]
Superficial layer is formed at least a portion of coat, and comprises and contain yttrium Y oxide.The formation of superficial layer can suppress the combination between the particle.And, comprise that the superficial layer that contains yttrium Y has the effect that helps above-mentioned coat.The situation that only forms coat is compared, and superficial layer has further suppressed surperficial wash-out activity.
Can be with the yttrium Y (based on the total amount of yttrium Y) that is no more than 20mol% in the oxide at least a metallic element substitution tables surface layer that is selected among magnesium Mg, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, aluminium Al, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W and the zirconium Zr.Should substitute the improvement of the diffusivity of the stability cause active material of cathode and lithium ion.
Based on the total amount of the yttrium Y in the oxide in the above-mentioned superficial layer, the amount of selected alternative metals element is no more than 20mol%, preferably is no more than 15mol%, and more preferably no more than 10mol%.When the amount of selected alternative metals element during greater than above-mentioned scope, it tends to reduce effect of the prevention sintering that brings by using of superficial layer and therefore reduces the effect that improves the charge-discharge cycles characteristic.
The amount of superficial layer is every m
2Application surface 1.0 * 10
-5Mole is to 1.0 * 10
-2The ruthenium ion of mole, this amount is counted as the amount of the yttrium Y that uses.
This amount is preferably from 3.0 * 10
-5Mole is to 5.0 * 10
-3Mole, and more preferably 1.0 * 10
-4Mole is to 1.0 * 10
-3Mole.When the amount of superficial layer during greater than above-mentioned scope, the diffusional resistance of lithium ion increases, and the capacity of final products active material of cathode of the present invention reduces.On the other hand, when this amount during less than above-mentioned scope, the effect that stops the effect of sintering and improve the charge-discharge cycles characteristic thus trends towards reduction.
The average particle size particle size of active material of cathode is that 2.0 μ m are to 50 μ m.When average particle size particle size during less than 2.0 μ m, in cathode fabrication process, peel off owing to pushing, thereby and because the conductive agent that the surface area increase needs increase of active material will be added and the amount of binding agent, so it trends towards reducing the energy density of per unit weight.On the other hand, when average particle size particle size during greater than 50 μ m, particle trends towards passing barrier film, causes short circuit thus.
[being used to make the method for active material of cathode]
Next, will method that make active material of cathode according to an embodiment of the invention be described.The method of making active material of cathode according to an embodiment of the invention is divided into two steps.In a first step, at least a portion of composite oxide particle, form the layer that comprises (one or more) hydroxide that contains nickel and/or manganese Mn, at least a portion of composite oxide particle, form the hydroxide that comprises yttrium Y then.In second step, after comprising the hydroxide of yttrium Y, formation heats composite oxide particle, so that at least a portion of composite oxide particle, form coat, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn, and comprises the superficial layer that contains yttrium Y oxide.
(first step)
In a first step, contain nickel and/or manganese Mn (one or more) hydroxide use processing, and comprise yttrium Y hydroxide use processing.According to first step, for example, at first, composite oxide particle is dispersed in the dicyandiamide solution that mainly comprises water, nickel compound and/or manganese Mn compound have been dissolved in this dicyandiamide solution, then, alkali is joined the medium basicity that increases this dispersion of this dispersion, thus (one or more) hydroxide of nickeliferous N i of precipitation and/or manganese Mn on the surface of composite oxide particle.In addition, composite oxide particle can be dispersed in the basic solvent that mainly comprises water, nickel compound and/or manganese Mn compound can be added in the aqueous solution then, precipitation contains nickel and/or manganese Mn (one or more) hydroxide thus.
The example of the parent material of nickel compound can comprise inorganic compound, for example nickel hydroxide, nickelous carbonate, nickel nitrate, nickel fluoride, nickel chloride, nickelous bromide, nickel iodide, nickelous perchlorate, bromic acid nickel, nickelous iodate, nickel oxide, nickel peroxide, nickel sulfide, nickelous sulfate, hydrogen nickel sulfide, nickel oxide, nickelous nitrite, nickel phosphate and nickel thiocyanide; And organic compound, for example nickel oxalate and nickel acetate.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
The example of the parent material of manganese Mn can comprise inorganic compound, for example manganous hydroxide, manganese carbonate, manganese nitrate, manganous fluoride, manganese chloride, manganous bromide, manganese iodide, chloric acid manganese, perchloric acid manganese, bromic acid manganese, Manganese diiodate, manganese oxide, manganese hypophosphite, manganese sulfide, hydrogen manganese sulfide, manganese nitrate, hydrogen sulfate manganese, thiocyanic acid manganese, nitrous acid manganese, manganese phosphate, phosphate dihydrogen manganese and bicarbonate manganese; And organic compound, for example manganese oxalate and manganese acetate.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
Next, will contain on the surface that yttrium Y hydroxide is administered to the composite oxide particle that is coated with (one or more) hydroxide that contains nickel and/or manganese Mn.Can be by containing the identical mode of nickel and/or manganese Mn (one or more) hydroxide and contain using of yttrium Y hydroxide with using.Just, the composite oxides that are coated with (one or more) hydroxide that contains nickel and/or manganese Mn are dispersed in the dicyandiamide solution that mainly comprises water, in this dicyandiamide solution, dissolved yttrium Y, and add in this dispersion or the like alkali to increase this dispersion basicity, precipitation contains the hydroxide of yttrium thus.The composite oxide particle that is coated with (one or more) hydroxide that contains nickel and/or manganese Mn can be dispersed in the basic solvent that mainly comprises water in addition, can in this basic solvent, add yttrium Y to be settled out its hydroxide.
The example of the parent material of yttrium Y compound can comprise inorganic compound, for example yttrium hydroxide, yttrium nitrate, yttrium fluoride, yttrium chloride, yttrium bromide, yttrium iodide, perchloric acid yttrium, yittrium oxide, yttrium sulfate and yttrium carbonate; And organic compound, for example yttrium oxalate and acetic acid yttrium.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
In a first step, the pH that mainly comprises the above-mentioned dicyandiamide solution of water is not less than pH 12, preferably is not less than pH 13, and more preferably is not less than pH 14.The pH of this dicyandiamide solution is high more, contain (one or more) hydroxide of nickel and/or manganese Mn and contain yttrium Y hydroxide to use uniformity good more, and the accuracy of reaction is high more.Therefore, improved productivity ratio owing to having shortened the processing time, and improved quality.Decide the pH of the dicyandiamide solution that mainly comprises water according to cost of the alkali that will use or the like.
In a first step, the temperature of dispersion is not less than 40 ℃ in processing procedure, preferably is not less than 60 ℃, more preferably is not less than 80 ℃.The temperature of dispersion is high more in the processing procedure, contain (one or more) hydroxide of nickel and/or manganese Mn and contain yttrium Y hydroxide to use uniformity good more, and reaction speed is fast more.Therefore, improved productivity ratio owing to having shortened the processing time, and improved quality.But owing to the processing time that causes in the improvement aspect the faster response speed shortening, so the uniformity of using from improvement and the viewpoint of productivity ratio, can preferably use autoclave under 100 ℃, to handle, although it is to determine according to the balance between equipment cost and the productivity ratio.
In addition, in a first step, for example, can in the dicyandiamide solution that mainly comprises water, on the composite oxide particle surface, form (one or more) hydroxide that contains nickel and/or manganese Mn, then particle is shifted out from the dicyandiamide solution that mainly comprises water, and the hydroxide that will comprise yttrium Y is administered on it, but the present invention is not limited to this.For example, can also on the surface of composite oxides, form (one or more) hydroxide that contains nickel and/or manganese Mn, then the hydroxide that comprises yttrium Y is added in the dicyandiamide solution, thereby the hydroxide that will comprise yttrium Y is administered on the particle, and particle is not separated from the dicyandiamide solution that mainly comprises water.
In addition, in a first step, can regulate the pH of the dicyandiamide solution that mainly comprises water by dissolving alkali in the dicyandiamide solution that mainly comprises water.The example of alkali can comprise lithium hydroxide, NaOH, potassium hydroxide and composition thereof.Although can regulate pH,, preferably use lithium hydroxide from the purity and the characteristic of the active material of cathode that obtains according to an embodiment by suitably using above-mentioned alkali.Using the advantage of lithium hydroxide is in the time will removing from the dicyandiamide solution that mainly comprises water through the composite oxide particle of using processing, can come the lithium amount in the control cathode active material by the amount of application of controlling the solvent that mainly comprises water.
(second step)
In second step, will separate with the dicyandiamide solution that mainly comprises water through using the composite oxide particle of processing in first step, the particle that obtains of heating is so that should multiple hydroxide dehydration then, thus formation coat and superficial layer.Preferably in the oxidizing atmosphere that is comprising air or pure oxygen under about 300 ℃ to 1000 ℃ temperature, heat-treat.In this case, apply (one or more) hydroxide contain nickel and/or manganese Mn with the hydroxide that contains yttrium Y, this can suppress the sintering between the particle and suppress combination between the particle.
At the composite oxide particle of using processing after separating from dicyandiamide solution that will carry out in first step, if necessary, for the amount of regulating lithium can heat the particle that obtains subsequently with the aqueous solution impregnated granules of lithium compound.
The example of lithium compound can comprise inorganic compound, for example lithium hydroxide, lithium carbonate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, lithium iodate, lithia, lithium peroxide, lithium sulfide, sulphur lithium hydride, lithium sulfate, lithium hydrogen sulfate, lithium nitride, Lithium Azide, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate and lithium bicarbonate; And organic compound, for example lithium methide, ethylidene lithium, isopropyl lithium, butyl lithium, phenyl lithium, lithium oxalate and lithium acetate.
After the calcining, in case of necessity, calomel mercurous chloride is broken by using, classification or the like, can regulate particle size.
Next, will the nonaqueous electrolyte battery that use according to the active material of cathode of an embodiment of the invention described above be described.
(3) the 3rd of rechargeable nonaqueous electrolytic battery the embodiment
(3-1) structure of rechargeable nonaqueous electrolytic battery
Fig. 5 has shown the cross-sectional structure that uses the rechargeable nonaqueous electrolytic battery of active material of cathode according to an embodiment of the invention.
Under fully charged state, this secondary cell has for example every target and anode is not less than 4.25V and is not more than 4.65V.
This secondary cell is so-called cylindrical battery, and has rolled electrode assembly 320 in the battery case 301 of hollow cylindrical substantially.In rolled electrode assembly 320, strip-shaped cathode 302 and ribbon anode 303 are reeled by barrier film 304.
The open end of battery case 301 is connected with battery cover 307, is formed on the relief valve device 308 and positive temperature coefficient element (PTC element) 309 of battery cover 307 inboards by pad 310 crimpings.The inside of sealed cell shell 301.Battery cover 307 is by for example constituting with battery case 301 identical materials.Relief valve device 308 is electrically connected with battery cover 307 by positive temperature coefficient element 309.When because internal short-circuit or when causing the internal pressure of battery to become being not less than certain value from the heat of outside, at this moment disc 311 rollbacks are with the electrical connection between cut-out battery cover 307 and the rolled electrode assembly 320.When temperature raise, positive temperature coefficient element 309 prevented the heat of the abnormal amount that big electric current causes thus by the resistivity Control current of increase.Pad 310 is to be made of for example surperficial insulating material that is covered with pitch.
The electrode assemblie 320 of reeling has for example center pin 312, around this center pin rolled electrode.Negative electrode 302 in the electrode assemblie 320 of reeling is connected with the cathode leg of being made by for example aluminium Al etc. 313, and anode 303 is connected with the anode tap of being made by for example nickel etc. 314.By being welded to relief valve device 308 cathode leg 313 is electrically connected to battery cover 307, and anode tap 314 is electrically connected to battery case 301 by welding.
[negative electrode]
Fig. 6 is the guide wire of alternative shape that shows the electrode assemblie 320 of coiling shown in Figure 5.As shown in Figure 6, negative electrode 302 has the cathode mixture layer 302B on cathode current collector 302A that for example has an opposite respect to one another and the both sides that are formed on cathode current collector 302A.Cathode mixture layer 302B can be formed on cathode current collector 302A only in the zone of a side.Cathode current collector 302A by metal forming for example for example aluminium foil constitute.Cathode mixture layer 302B comprises for example active material of cathode, and can comprise for example graphite and binding agent polyvinylidene fluoride for example of conductive agent if desired.As active material of cathode, can use active material of cathode according to above-mentioned embodiment.
[anode]
As shown in Figure 6, anode 303 has the anode collector 303A that for example has an opposite respect to one another and is formed on anode mixture layer 303B on the both sides of anode collector 303A.Anode mixture layer 303B can be formed on anode collector 303A only in the zone of a side.Anode collector 303A is made of for example metal forming such as Copper Foil.Anode mixture layer 303B comprises for example active material of positive electrode, and can comprise for example polyvinylidene fluoride of binding agent if desired.
Active material of positive electrode comprises the anode material (hereinafter, being sometimes referred to as " anode material that can absorb/discharge lithium Li ") that can absorb and discharge lithium Li.The nitride that the example that can absorb/discharge the anode material of lithium Li can comprise material with carbon element, metallic compound, oxide, sulfide, lithium is LiN for example
3, the lithium metal, form the metal and the polymeric material of alloy with lithium.
The example of material with carbon element can comprise low graphited carbon, easy graphited carbon, graphite, RESEARCH OF PYROCARBON, coke, vitreous carbon, organic polymer compounds sintered body, carbon fiber and activated carbon.Wherein, coke can comprise pitch coke, needle coke and petroleum coke.Organic polymer compounds sintered body refers to by for example phenol plastics or furane resins are divided into low graphitized carbon or easy graphited carbon with in these materials some making it the material that carbonization obtains at suitable temperature lower calcination polymeric material.The example of polymeric material can comprise polyacetylene and polypyrrole.
In can absorbing/discharge these anode materials of lithium Li, preferred charging and discharge voltage approach the charging of lithium metal and the material of discharge voltage.This is because the charging and the discharge voltage of anode 303 is low more, and battery is easy more to have higher energy density.Wherein, material with carbon element is preferred, because their crystal structure has only little variation when charging and discharge, therefore, can obtain good cycle characteristics and big charging and discharge capacity.Especially preferred graphite is because it can provide big electrochemical equivalent and high energy density.Low graphitized carbon also is preferred, because it can provide good cycle characteristics.
In addition, the anode material that can absorb/discharge lithium Li can comprise simple substance lithium metal, can form the metallic element and the semimetallic elements of alloy with lithium Li together, comprises the alloy of such element and compound or the like.They are preferred, because they can provide high-energy-density.Especially, more preferably they and material with carbon element are used together,, can obtain good cycle characteristics and high-energy-density because in this case.Except the alloy that comprises two kinds or more of metallic elements, alloy used herein also comprises the alloy that comprises one or more metallic elements and one or more semimetallic elements.This alloy can be in following state solid solution, eutectic crystal (eutectic mixture), intermetallic compound and composition thereof.
The example of metallic element and semimetallic elements can comprise tin Sn, plumbous Pb, aluminium Al, indium In, silicon Si, zinc Zn, antimony Sb, bismuth Bi, cadmium Cd, magnesium Mg, boron, gallium Ga, germanium Ge, arsenic As, silver-colored Ag, zirconium Zr, yttrium Y and hafnium Hf.The example of above-mentioned alloy and compound can comprise having chemical formula: Ma
sMb
tLi
uMaterial and have chemical formula a: Ma
pMc
qMd
rMaterial.In these chemical formulas, Ma represents and can form the metallic element of alloy and at least a element in the semimetallic elements with lithium; Mb represents metallic element except that lithium and Ma and at least a element in the semimetallic elements; Mc represents at least a element in the nonmetalloid; Md represents metallic element except that Ma and at least a element in the semimetallic elements; And s, t, u, p, q and r satisfy s＞0, t 〉=0, u 〉=0, p＞0, q＞0 and r 〉=0.
Wherein, the metallic element and the semimetallic elements of preferred IVB family short period table, and the alloy and the compound that comprise such element, and preferred especially silicon Si, tin Sn and comprise Si and/or the alloy of Sn and compound.They can be crystal or amorphous.
In addition, can in negative electrode or anode, use the inorganic compound that does not comprise lithium Li, for example MnO
2, V
2O
5, V
6O
13, NiS and MoS.
[electrolyte solution]
As electrolyte solution, can use the non-aqueous electrolytic solution that obtains by dissolving electrolytic salt in nonaqueous solvents.For example, preferred nonaqueous solvents can be for example to comprise solvent at least a in ethylene carbonate and the propylene carbonate, because they can improve cycle characteristics.Especially preferred is the mixture that comprises ethylene carbonate and propylene carbonate in electrolyte, because can further improve cycle characteristics.Nonaqueous solvents preferably includes at least a ester that is selected from the linear carbonate, and for example diethyl carbonate, dimethyl carbonate, ethylene methyl esters and carbonic acid first propyl ester are because they can further improve cycle characteristics.
Comprise 2, at least a nonaqueous solvents also is preferred in 4-difluoroanisole and the vinylene carbonate, because 2, the 4-difluoroanisole can improve discharge capacity, and vinylene carbonate can improve cycle characteristics.The nonaqueous solvents that more preferably comprises its mixture is because can improve discharge capacity and cycle characteristics.
Nonaqueous solvents can also comprise following at least a compound: butylene carbonate, gamma-butyrolacton, gamma-valerolactone, the compound that its (one or more) oh group is replaced by fluoro-containing group in whole or in part, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, 1, the 3-dioxolane, the 4-methyl isophthalic acid, the 3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxy-propyl nitrile, N, dinethylformamide, the N-methyl pyrrolidone, the N-methyl oxazolidinone, N, N-methylimidazole alkane ketone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide (DMSO) and trimethyl phosphate.
In some cases, can improve the invertibity of electrode reaction by using the material that comprises in the above-mentioned nonaqueous solvents, according to will in conjunction with electrode, (one or more) hydroxyl of this material is replaced in whole or in part by fluorine atom.Can suitably use these materials.
Suitable example as the lithium salts of electrolytic salt can comprise LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiCl, LiBF
2(ox) difluoro lithium borate (oxalato), LiBOB and LiBr.They can use separately or can use its mixture.Wherein, LiPF
6Be preferred, because it can provide high ionic conductivity and improve cycle characteristics.
[barrier film]
Now, will the diaphragm material that can use be described in the nonaqueous electrolyte battery of use according to the active material of cathode of an embodiment.As diaphragm material, can use the material that has been used for conventional batteries.In them, especially preferably use microporous polyolefin film, they have good effect to preventing short circuit, and can be by turn-offing the stability of effect improving battery.For example, the microporous barrier of preferably making by polyvinyl resin or acrylic resin.
As diaphragm material, from the viewpoint of well balanced turn-off performance and flotation property, also preferred the use has low polyacrylic duplexer or the mixture that turn-offs the polyethylene of temperature and have highly-acidproof.
(3-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, will method that make rechargeable nonaqueous electrolytic battery be described.To be that example is described this method with cylindrical rechargeable nonaqueous electrolytic battery.
Manufacturing negative electrode 302 as described below.At first, for example active material of cathode, conductive agent and binding agent are mixed with the preparation cathode mix, then the cathode mix that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of cathode mix.
Subsequently, the slurry of cathode mix is coated on the cathode current collector 302A, and dry solvent, uses roll squeezer etc. to suppress moulding then, form cathode mixture layer 302B, constitute negative electrode 302 by this cathode mixture layer.
Following manufacturing anode 303.At first, for example active material of positive electrode and binding agent are mixed with the preparation anode mixture, then the anode mixture that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of anode mixture.
Subsequently, the slurry of anode mixture is coated on the anode collector 303A, and dry solvent, uses roll-in manufacturing type etc. to suppress moulding then, form anode mixture layer 303B, constitute anode 303 by this anode mixture layer.
Next, cathode leg 313 is connected to cathode current collector 302A by for example welding, and by the welding etc. anode tap 314 is connected to anode collector 303A.Then, by barrier film 304 coiling negative electrodes 302 and anode 303, and the leading section of cathode leg 313 is welded to relief valve device 308, the leading section with anode tap 314 is welded to battery case 301 simultaneously.Then, the negative electrode 302 and the anode 303 of reeling is clipped between a pair of insulation board 305 and 306, it is contained in the battery case 301.
Then, electrolyte solution is injected battery case 301, use electrolyte solution impregnation barrier film 304 thus.Subsequently, battery cover 307, relief valve device 308 and positive temperature coefficient element 309 by the open end crimping of pad 310 at battery case 301, so that they are fixed, thereby are made rechargeable nonaqueous electrolytic battery.
(4) the 4th of rechargeable nonaqueous electrolytic battery the embodiment
(4-1) structure of rechargeable nonaqueous electrolytic battery
Fig. 7 has shown the structure of using the rechargeable nonaqueous electrolytic battery of active material of cathode according to an embodiment of the invention.As shown in Figure 7, rechargeable nonaqueous electrolytic battery has such structure, and wherein cell device 330 is contained in the clad material of being made by moistureproof stack membrane 337, and the periphery of welding cell device 330 is with sealing.Cell device 330 has cathode leg 332 and anode tap 333 and these lead-in wire encapsulated materials 337 and is clipped in the middle and is drawn out to the outside.The both sides of cathode leg 332 and anode tap 333 are all covered by resin sheet 334 and resin sheet 335, so that improve the attachment characteristic to clad material 337.
[clad material]
[cell device]
Are coiling cell devices 330 by cell device shown in Figure 8 330 for example, it is stacked and reel at longitudinal direction wherein will to have ribbon anode 343, the barrier film 344 of the gel electrolyte layer 345 that is formed on its both sides, the strip-shaped cathode 342 with the gel electrolyte layer 345 that is formed on its both sides and a barrier film 344.
End at negative electrode 342 forms cathode leg 332 at longitudinal direction, and it is connected to electrode by spot welding or ultra-sonic welded.As the material of cathode leg 332, can use for example metal of aluminium.
Be similar to negative electrode 342, form anode tap 333 at an end of anode 343 at longitudinal direction, it is connected to electrode by spot welding or ultra-sonic welded.Can use the material of the metal of copper Cu for example or nickel as anode tap 333.
Therefore the same in parts except gel electrolyte layer 345 and first embodiment will describe gel electrolyte layer 345 below.
The example of polymer compound can comprise copolymer, polytetrafluoroethylene, polyhexafluoropropylene, poly(ethylene oxide), PPOX, poly phosphazene, polysiloxanes, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, acrylonitrile-butadiene rubber, polystyrene and the Merlon of polyacrylonitrile, polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene.From the viewpoint of electrochemical stability, special optimization polypropylene nitrile, polyvinylidene fluoride, polyhexafluoropropylene and poly(ethylene oxide).
(4-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, make the method for rechargeable nonaqueous electrolytic battery with describing the active material of cathode that uses according to an embodiment of the invention.At first, with comprising the precursor solution coated cathode 342 of solvent, electrolytic salt, polymer compound and mixed solvent and each of anode 343, evaporate mixed solvent then to form gel electrolyte layer 345.By welding the end that cathode leg 332 is connected in advance cathode current collector, simultaneously, also anode tap 333 is connected to the end of anode collector 343A by welding.
Subsequently, by barrier film 344 that negative electrode 342 and anode 343 is stacked, all formed gel electrolyte layer 345 on negative electrode 342 and the anode 343, and the longitudinal direction that is stacked in that will obtain reels, to form coiling cell device 330.
Next, the clad material 337 that is made of stack membrane is drawn to form recessed portion 336.Then, cell device 330 is incorporated in the recessed portion 336, the unprocessed portion of clad material 337 is bent to the top of recessed portion 336, the periphery that welds recessed portion 336 is then made rechargeable nonaqueous electrolytic battery thus with sealing.
[embodiment]
To describe according to embodiment of the present invention by means of embodiment, but the present invention is not limited to this.
＜embodiment 6 〉
At first, by stirring 1 hour down at 80 ℃, the composite oxide particle of 10 weight portions is dispersed in the 2N LiOH aqueous solution of 300 weight portions, this composite oxide particle has average composition Li
1.03CoO
2.02, the 13 μ m that measure by laser scattering method average particle size particle size and 0.3m
2The specific area of/g.
Then, will be in 2 hours by dissolving 1.54 weight portion commercial reagents nitric acid nickel (NO in 10 parts by weight of purified water
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 0.83 weight portion
3)
26H
2The solution that O obtains adds to wherein.
Then, will be in 1 hour by the commercial reagents yttrium nitrate Y (NO of dissolving 0.20 weight portion in 5 parts by weight of purified water
3)
36H
2The solution that O obtains adds to wherein, and this mixture of stirring made its cooling to disperse in other 1 hour under 80 ℃.
Subsequently, filter this dispersion, and dry down at 120 ℃.In order to regulate the amount of lithium, flood the precursor sample of 10 weight portions with the 2N LiOH aqueous solution of 2 weight portions, and evenly mix this mixture, and the dry precursor that is used to calcine of obtaining.The temperature of the precursor that will be used to calcine with the speed of 5 ℃ of per minutes in electric furnace is elevated to 950 ℃, and protects special 5 hours under this temperature, and the speed with 7 ℃ of per minutes is cooled to 150 ℃ then, obtains the active material of cathode of embodiment 6.
＜embodiment 7 〉
Make active material of cathode in the mode identical with embodiment 6, difference is the nitric acid nickel (NO that will add
3)
26H
2The quantitative change of O turns to 3.08 weight portions; With the manganese nitrate Mn (NO that adds
3)
26H
2The quantitative change of O turns to 3.30 weight portions; With the Y (NO that adds
3)
36H
2The quantitative change of O turns to 0.80 weight portion; The quantitative change that is used to dissolve the pure water of nickel nitrate and manganese nitrate turns to 5 weight portions; And the quantitative change of the 2N lithium hydroxide aqueous solution that is used to flood for the amount of regulating lithium turns to 5 weight portions.
＜embodiment 8 〉
Making the active material of cathode of embodiment 8 with the same way as of embodiment 6, difference is the nitric acid nickel (NO that will add
3)
26H
2The quantitative change of O turns to 3.08 weight portions; With the manganese nitrate Mn (NO that adds
3)
26H
2The quantitative change of O turns to 1.65 weight portions; With the Y (NO that adds
3)
36H
2The quantitative change of O turns to 0.80 weight portion; The quantitative change that is used to dissolve the pure water of nickel nitrate and manganese nitrate turns to 20 weight portions; And the quantitative change of the 2N lithium hydroxide aqueous solution that is used to flood for the amount of regulating lithium turns to 4 weight portions.
＜comparative example 3 〉
The same compound oxide particle that uses among use and the embodiment 6 is 3 active material of cathode as a comparative example, and this composite oxide particle has average composition Li
1.03CoO
2.02, the 13 μ m that measure by laser scattering method average particle size particle size and 0.3m
2The specific area of/g.
＜comparative example 4 〉
Remove and do not add Y(NO
3)
39H
2Outside the O, make the active material of cathode of comparative example 4 in the mode identical with embodiment 6.
Measure:
Use the active material of cathode of making in embodiment 6 to 8 and comparative example 3 and 4, the secondary cell shown in the shop drawings 5 and 6.At first, the prepared cathode active material powder, 10wt% of mixing 86wt% be as the graphite of conductive agent and the 4wt% polyvinylidene fluoride as binding agent, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-.Then, this dispersion is coated on the cathode current collector 302A both sides that are made of the thick banded aluminium foil of 20 μ m, and with the collector drying that obtains.Subsequently, form cathode mixture layer 302B, make negative electrode 302 thus by using roll squeezer to suppress moulding.At this moment, thoroughly pulverize cathode active material powder, so that pass filter screen with 70 μ m apertures with kneading machine.The porosity of cathode mixture layer 302B is controlled to be 26% volume ratio.Next, aluminium cathode leg 313 is connected to cathode current collector 302A.
In addition, 90wt% is mixed as the polyvinylidene fluoride of binding agent as the Delanium powder of active material of positive electrode and 10wt%, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-.Then, this dispersion is coated on the anode collector 303A both sides that are made of the thick banded Copper Foil of 10 μ m, and with the collector drying that obtains.Subsequently, form anode mixture layer 303B, make anode 303 thus by using roll squeezer to suppress moulding.Next, nickel anode lead-in wire 314 is connected to anode collector 303A.
The strip-shaped cathode 302 and the ribbon anode 303 that obtain are thus much enclosed by reeling as the porous polyolefin membrane of barrier film 304, so that make the electrode assemblie 320 of screw winding.The electrode assemblie 320 of reeling is contained in the battery case 301 of irony, and a pair of insulation board 305 and 306 is placed on the top side and bottom side of rolled electrode assembly 320.Then, cathode leg 313 is guided to cathode current collector 302A outside, and be welded to relief valve device 308, similarly, anode tap 314 is guided to anode collector 303A outside, and be welded to the bottom of battery case 301.Thereafter, electrolyte solution is injected into the inside of battery case 301, and carry out crimping by pad 310 battery cases 301, with fixedly relief valve device 308, positive temperature coefficient element 309 and battery cover 307, obtain to have the column secondary battery of 18mm overall diameter and 65mm height thus.As electrolyte solution, use electrolytic salt LiPF by dissolving 1.0mol/l in the solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1)
6The solution that obtains.
The secondary cell of so making is charged under 45 ℃ of temperature and discharge, determine initial capacity and discharge capacitance thus, this initial capacity is the discharge capacity of the circulation time first time, and this discharge capacitance is the ratio in discharge capacity with the discharge capacity that circulates for the first time of the 200th circulation.
Carry out constant current charge by constant current and reach 4.40V, carry out constant voltage charge with the constant voltage of 4.40V then and reach 2.5 hours up to total charging interval and carry out charging up to cell voltage with 1000mA.Carry out constant-current discharge by constant current and till the cell voltage that reaches 2.75V, carry out discharge with 800mA.In measurement result shown in the table 2.
[table 2]
| Initial capacity (mAh) | Discharge capacitance (%) | |
| Embodiment 6 | 2420 | 82 |
| Embodiment 7 | 2460 | 83 |
| Embodiment 8 | 2450 | 85 |
| Comparative example 3 | 2510 | 30 |
| Comparative example 4 | 2450 | 79 |
As shown in table 2, should be understood that capacity that the battery of the active material of cathode that use obtains is high and ratio use the higher discharge capacitance of battery of the active material of cathode that obtains in the comparative example 3 and 4 in embodiment 6 to 8.
The present invention is not limited to above-mentioned embodiment of the present invention, can make various deformation and application under the condition that does not break away from the scope of the invention.For example, its shape is restriction especially not, can use cylindrical shape type, square type, Coin shape, button type or the like.
In the 3rd embodiment, rechargeable nonaqueous electrolytic battery with electrolyte solution as electrolyte, and in the 4th embodiment, rechargeable nonaqueous electrolytic battery with gel electrolyte as electrolyte.Yet the present invention is not limited to this.
For example, not only can use above-mentioned electrolyte, but also can use the copolymer solid electrolyte that utilizes ionic conductive polymer, the inorganic solid electrolyte of utilizing the ionic conduction inorganic material is as electrolyte.And they can use separately or conduct is used with the electrolytical mixture of another kind.The example that is used for the polymer compound of solid polyelectrolyte can comprise polyethers, polyester, polyphosphazene and polysiloxanes.The example of inorganic solid electrolyte can comprise ionic conductivity ceramics, from conductive crystal and ionic conducting glass.
And for example, the electrolyte solution in the rechargeable nonaqueous electrolytic battery has no particular limits, and can use the electrolyte solution of conventional non-aqueous solvent system.Wherein, the preferred example of the non-aqueous electrolytic solution that comprises alkali metal salt in the secondary cell comprises propylene carbonate, ethylene carbonate, gamma-butyrolacton, N-methyl pyrrolidone, acetonitrile, N, dinethylformamide, methyl-sulfoxide, oxolane, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxy-ethane, carbonic acid two ethyls, its derivative and composition thereof.The electrolytical preferred example that comprises in the electrolyte solution comprises alkali metal, especially calcium halide, perchlorate, rhodanate, borofluoride, fluorophosphate, fluoridize arsenic, yttrium fluoride and trifluoromethyl sulfate.
Now, explain the the 7th, the 8th and the 9th embodiment of the present invention with reference to the accompanying drawings.Active material of cathode according to an embodiment of the invention has the coat at least a portion of composite oxide particle, this layer comprises (one or more) oxide that contains lithium Li oxide and contain (one or more) coating element of nickel or nickel and manganese Mn, and have superficial layer at least a portion of coat, this superficial layer comprises vanadium V.
At first, will explain that active material of cathode has the reason of said structure.Mainly comprise cobalt acid lithium LiCoO
2Active material of cathode have high charge voltage characteristic and corresponding high-energy-density characteristic, but under the high power capacity of high charge voltage recharge and discharge cycles, their capacity significantly reduces.This reduction is the surface state because of active material of cathode, thereby has pointed out the surface-treated necessity of active material of cathode.
Therefore, the kinds of surface processing has been proposed.Never reduce the capacity of every volume or weight or minimize the viewpoint that capacity reduces, reduce or be coated with by the inhibition capacity and help suppress the surface and go up the material that capacity reduces, can obtain to have high charge voltage characteristic and corresponding energy density characteristics, and when high charge voltage the active material of cathode of good charge-discharge cycles characteristic.
Result as inventor's further investigation, have been found that to obtain to have high charge voltage characteristic and corresponding high-energy-density characteristic (though they are lower slightly), and the active material of cathode of the good charge-discharge cycles characteristic of high power capacity under the high charge voltage conditions.By mainly comprising cobalt acid lithium LiCoO
2Active material of cathode on form and to comprise that the coat that contains lithium Li oxide and contain (one or more) oxide of at least a coating element among nickel and the manganese Mn obtains this active material of cathode.
Method as form cathode layer on composite oxide particle can propose following two kinds of methods.In one approach, lithium Li compound and nickel compound and/or manganese Mn compound and composite oxide particle are ground to obtain fine particle, and they are done mixed, use each other, and calcining, so that form coat on the surface of composite oxide particle, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn.In another approach, lithium Li compound and nickel compound and/or manganese Mn compound be dispersed in the solvent or and solvent, and carry out wet-applying and calcining, so that form coat on the surface of this composite oxide particle, this coat comprises (one or more) oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn.Yet the result that these methods obtain is possible to obtain the coat of high uniformity.
The inventor has further advanced their further investigation, and finds (one or more) hydroxide by using nickel and/or manganese Mn and make the product dehydration that obtains form coat with the coat that generation has high uniformity by heating.Use processing according to this, dissolving nickel compound and/or manganese Mn compound in the dicyandiamide solution that mainly comprises water, in dicyandiamide solution, disperse composite oxide particle then, and add in the dispersion or the like alkali to improve dispersion basicity, precipitation contains (one or more) hydroxide of nickel and/or manganese Mn on the surface of composite oxide particle thus.
Make through using the composite oxide particle dehydration that the hydroxide that contains nickel and/or manganese Mn is used in processing, so that on composite oxide particle, form coat by heating.This can improve the uniformity of the coat on the composite oxide particle.
The inventor has further advanced their further investigation, and have been found that (one or more) hydroxide that will contain nickel and/or manganese Mn be administered to the composite oxide particle surface and to the particle that obtains clean, dehydration and dry so that in the step of calcining, particle is bonded to each other by being applied in lip-deep (one or more) hydroxide that contains nickel and/or manganese Mn; And when the breakage of particles of combination, because relatively low bonding characteristic, the interface occurring between (one or more) hydroxide that contains nickel and/or manganese Mn and composite oxide particle peels off, perhaps because low bonding force, in the hydroxide that contains nickel and/or manganese Mn, adhesion failure occurs, thereby damaged the improvement of the characteristic of the active material of cathode that brings by the formation coat.
And, the inventor also finds, if under situation about existing, proceed wherein to add the calcination process of lithium Li in conjunction with particle, perhaps have in its surface in the state that the particle of (one or more) hydroxide that contains nickel and/or manganese Mn contacts with each other, the sintering between the particle is tending towards easier to carry out.
When the sintering between the particle carry out excessive the time, following problem appears.When forming negative electrode, need to increase and be used to break the input of mechanical energy of particle, carry out this breakage of particles and be used for hybrid particles and binding agent and conductive agent carbon granule equably.Therefore, the active material of cathode that comprises the composite oxide particle with coat is damaged or break, cause the increase of defect particles total number.
When the coupling part between the sintered particles is broken, formed the fracture of crack, particle, coat and peels off or the like in particle, take place to lose efficacy or fracture.Especially, with mainly comprise cobalt acid lithium LiCoO
2Active material of cathode compare, the composite oxide particle with coat tends to have a non-planar surface, rather than level and smooth surface.Because this structure, when when they apply external force, particle may be difficult to slide on each other, and on external force is easy to concentrate on a little, therefore occurs easily losing efficacy or rupturing.
As a result, exposed the surface that does not form coat.In other words, exposed the surface and the active newly-generated surface that do not have coat, this does not have the surface of coat can not play the effect that improves the charge-discharge cycles characteristic.Charge-discharge cycles deterioration in characteristics under high power capacity high charge voltage conditions.The surface of exposing as is known, is active and has high surface energy.Therefore, compare with the surface that forms in the common calcining, this surface has very high activity and wash-out activity in the decomposable process of electrolyte solution.
In order to improve cathode function and production technology, the inventor has advanced further investigation based on the sintering between the particle, and have been found that, when the composite oxide particle of further (one or more) hydroxide that contains nickel or nickel and manganese Mn having been used on the surface is used molybdic acid, can improve the process of sintering.Also find, can reduce the inefficacy or the fracture of particle.Next, composite oxides, coat and superficial layer will be described.
[composite oxides]
Composite oxide particle has average composition of for example being represented by formula 1.Composite oxide particle has average composition the by formula 1 expression, therefore can have high power capacity and high discharge voltage.
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
In formula 1, x is in the scope of-0.10≤x≤0.10, and is preferred-0.08≤x≤0.08, and more preferably-0.06≤x≤0.06.When the value of x during less than above-mentioned scope, discharge capacity may reduce.When the value of x during greater than above-mentioned scope, lithium can diffuse out from particle, and may damage with the control of the basicity in the post-processing step, the adverse effect that when finally causing kneading cathode paste gelation is promoted.
Y in the scope of 0≤y＜0.50, preferred 0≤y＜0.40, and more preferably 0≤y＜0.30.When the value of y during, can damage LiCoO greater than above-mentioned scope
2The high charge voltage characteristic that is had, and corresponding high-energy-density characteristic.
Z is in the scope of-0.10≤z≤0.20, and is preferred-0.08≤z≤0.18, and more preferably-0.06≤z≤0.16.When the value of z less than or during greater than above-mentioned scope, it trends towards reducing discharge capacity.
Although the material that can be used as active material of cathode usually can be as the parent material of composite oxide particle, in some cases, can use by utilizing the break particle of second particle acquisition of ball mill, kneading machine or the like.
[coat]
Coat is formed at least a portion of composite oxide particle, and comprises (one or more) oxide that contains lithium Li oxide and contain (one or more) coating element of nickel or nickel and manganese Mn.The formation of this coat produces high charge voltage characteristic and corresponding high-energy-density characteristic, and can improve the charge-discharge cycles characteristic under the high charge voltage conditions of high power capacity.
The proportion of composing of nickel and manganese Mn is preferably in 100: 0 to 30: 70 scope in the coat, and more preferably 100: 0 to 40: 60.The amount of manganese Mn is big more, and holding of lithium Li stays characteristic low more, finally causes when use the reduction of the capacity of active material of cathode at that time and the increase of resistance in battery.The above-mentioned scope of the proportion of composing of nickel and manganese Mn is the scope that shows better efficient, in other words, in this scope, is added with in the process of precursor of lithium Li in calcining, has suppressed the carrying out of the sintering between the particle.
Can substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W.
Should alternatively make and to improve the stability of active material of cathode and the diffusivity of lithium ion.The amount of selected alternative metals element is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat, preferably is no more than 30mol%, and more preferably no more than 20mol%.If the amount of selected alternative metals element is greater than above-mentioned scope, then lithium Li's holds the capacity that stays characteristic and active material of cathode and may reduce.
The amount of coat be the 0.5wt% of composite oxide particle to 50wt%, preferred 1.0wt% is to 40wt%, more preferably 2.0wt% is to 35wt%.This is because when the amount of coat during greater than above-mentioned scope, the capacity reduction of active material of cathode; Yet when the amount of coat during less than above-mentioned scope, the stability of active material of cathode reduces.
[superficial layer]
Superficial layer is formed at least a portion of coat, and comprises vanadium V.The formation of superficial layer can suppress the combination between the particle.And, comprise that the superficial layer of vanadium V has the effect that helps above-mentioned coat.The situation that only forms coat is compared, and superficial layer has further suppressed surperficial wash-out activity.
The average particle size particle size of active material of cathode is that 2.0 μ m are to 50 μ m.When average particle size particle size during less than 2.0 μ m, in cathode fabrication process, peel off owing to pushing, thereby and because the conductive agent that the surface area increase needs increase of active material will be added and the amount of binding agent, so it tends to reduce the energy density of per unit weight.On the other hand, when average particle size particle size during greater than 50 μ m, particle tends to pass barrier film, causes short circuit thus.
[being used to make the method for active material of cathode]
Next, will method that make active material of cathode according to an embodiment of the invention be described.The method of making active material of cathode according to an embodiment of the invention is divided into two steps.In a first step, at least a portion of composite oxide particle, form the layer that comprises (one or more) hydroxide that contains nickel or nickel and manganese Mn, vanadic acid is administered at least a portion of composite oxide particle then.In second step, the heating composite oxide particle is so that form coat at least a portion of composite oxide particle after using vanadic acid, this coat comprises and contains lithium Li oxide and contain (one or more) oxide that (one or more) apply element nickel or nickel and manganese Mn, and the superficial layer that comprises vanadium V.
(first step)
In a first step, contain nickel or nickel and manganese Mn (one or more) hydroxide use processing, and vanadic acid use processing.According to first step, for example, at first composite oxide particle is dispersed in the dicyandiamide solution that mainly comprises water, dissolved the nickel compound in this dicyandiamide solution, perhaps nickel compound and manganese Mn compound, then, alkali is joined the medium basicity that increases this dispersion of dispersion, on the surface of composite oxide particle, precipitate (one or more) hydroxide that contains nickel or nickel and manganese Mn thus.In addition, composite oxide particle can be dispersed in the basic solvent that mainly comprises water, then can be with the nickel compound, perhaps nickel and manganese Mn compound add in this aqueous solution, can be settled out (one or more) hydroxide that contains nickel or nickel and manganese Mn thus.
The example of the parent material of nickel compound can comprise inorganic compound, for example nickel hydroxide, nickelous carbonate, nickel nitrate, nickel fluoride, nickel chloride, nickelous bromide, nickel iodide, nickelous perchlorate, bromic acid nickel, nickelous iodate, nickel oxide, nickel peroxide, nickel sulfide, nickelous sulfate, hydrogen nickel sulfide, nickel oxide, nickelous nitrite, nickel phosphate and nickel thiocyanide; And organic compound, for example nickel oxalate and nickel acetate.Can in statu quo use them, perhaps in case of necessity, with processing such as acid so that change into the compound that can be dissolved in the dicyandiamide solution.
The example of the parent material of manganese Mn can comprise inorganic compound, for example manganous hydroxide, manganese carbonate, manganese nitrate, manganous fluoride, manganese chloride, manganous bromide, manganese iodide, chloric acid manganese, perchloric acid manganese, bromic acid manganese, Manganese diiodate, manganese oxide, manganese hypophosphite, manganese sulfide, sulphur hydrogenation manganese, manganese nitrate, hydrogen sulfate manganese, thiocyanic acid manganese, nitrous acid manganese, manganese phosphate, phosphate dihydrogen manganese and bicarbonate manganese; And organic compound, for example manganese oxalate and manganese acetate.Can in statu quo use them, perhaps in case of necessity, change into the compound that can be dissolved in the dicyandiamide solution with processing such as acid.
The above-mentioned pH that mainly comprises the dicyandiamide solution of water is not less than pH 12, preferably is not less than pH 13, and more preferably is not less than pH 14.The pH of dicyandiamide solution that mainly comprises water is high more, contain nickel or nickel and manganese Mn (one or more) hydroxide to use uniformity good more, and the accuracy of reaction is high more.Therefore, because the processing time that shortens, thereby improved productivity ratio, and improved quality.Decide the pH of the dicyandiamide solution that mainly comprises water according to cost of the alkali that will use or the like.
The temperature of dispersion is not less than 40 ℃ in processing procedure, preferably is not less than 60 ℃, and more preferably is not less than 80 ℃.The temperature of dispersion is high more in the processing procedure, contain nickel or nickel and manganese Mn (one or more) hydroxide to use uniformity good more, and reaction speed is high more.Therefore, because the processing time that shortens, thereby improved productivity ratio, and improved quality.Because the improvement of faster response speed causes reduction in processing time, so the uniformity of using from improvement and the viewpoint of productivity ratio, can preferably use autoclave under 100 ℃, to handle, although it is to determine according to the balance between equipment cost and the productivity ratio.
Can regulate the pH of the dicyandiamide solution that mainly comprises water by dissolving alkali in the dicyandiamide solution that mainly comprises water.The example of alkali can comprise lithium hydroxide, NaOH, potassium hydroxide and composition thereof.Although by suitably using above-mentioned alkali to carry out the adjusting of pH,, preferably use lithium hydroxide from purity and characteristic according to the gained active material of cathode of an embodiment.Use the advantage of lithium hydroxide to be, when the composite oxide particle that forms (one or more) hydroxide comprise nickel or nickel and manganese Mn is thereon taken out from the dicyandiamide solution that mainly comprises water, can control according to the lithium amount in the gained active material of cathode of an embodiment by the amount of application of controlling the solvent that mainly comprises water.
Subsequently, vanadic acid is administered to thereon to form comprises and contain nickel, perhaps at least a portion of the composite oxide particle of (one or more) hydroxide of nickel and manganese Mn.Under vanadic acid is suspended in state in the dicyandiamide solution that mainly comprises water, carry out the processing of using of vanadic acid effectively, this dicyandiamide solution that mainly comprises water be used to contain nickel or nickel and manganese Mn hydroxide use processing.By using this system, to the composite oxides that are formed with the layer that comprises (one or more) hydroxide of containing nickel or nickel and manganese Mn on it dewater and dry step in, can suppress the combination of particle by this lip-deep (one or more) hydroxide that contains nickel or nickel and manganese Mn.
And, effectively carry out the processing of using of vanadic acid in the cleaning step after using of the hydroxide that contains nickel or nickel and manganese Mn handled.Utilize this method to make to prevent the leakage of the vanadic acid that adds suspension system to, and improve absorption characteristic.And, by using the processing of using of molybdic acid, can obtain to promote the effect of particle aggregation, and can not cause the combination between the particle in the suspended substance system, thereby can easily clean and reclaim the particle that comes self-dispersing system.
As vanadic acid, can use vanadic acid arbitrarily, for example ortho-vanadic acid, pyrovanadic acid and metavanadic acid.The example of the parent material of the vanadic acid that can use in using processing can comprise lithium metavanadate, metavanadic acid magnesium, ammonium metavanadate, metavanadic acid caesium, ortho-vanadic acid caesium, potassium metavanadate, ortho-vanadic acid potassium, sodium metavanadate, sodium orthovanadate, vanadic acid and vanadic acid anhydride.
Based on the weight of composite oxide particle, the amount of the vanadic acid of using is from 0.00001wt% to 1.0wt%.This amount is preferably 0.0001wt% to 0.1wt%.When the amount of the vanadic acid of using during greater than above-mentioned scope, the capacity of active material of cathode reduces.When the amount of the vanadic acid of using during less than above-mentioned scope, the stability of active material of cathode reduces.
(second step)
In second step, to separate through the composite oxide particle of using processing in first step and the dicyandiamide solution that mainly comprises water, the particle that obtains of heating is so that the dehydration of (one or more) hydroxide then, thereby on the surface of composite oxide particle, form coat, this coat comprises and contains lithium Li oxide, with (one or more) oxide that contains (one or more) coating element nickel or nickel and manganese Mn, and the superficial layer that comprises vanadium.Preferably in the oxidizing atmosphere that is comprising air or pure oxygen under about 300 ℃ to 1000 ℃ temperature, heat-treat.In this case, because vanadic acid is attached on (one or more) hydroxide that contains nickel or nickel and manganese Mn, so suppressed sintering between the particle and the combination between the particle.
With the composite oxide particle of using processing and the dicyandiamide solution after separating that passes through in first step, if necessary, for the amount of regulating lithium can heat the particle that obtains subsequently with the aqueous solution impregnated granules of lithium compound.
The example of lithium compound can comprise inorganic compound, for example lithium hydroxide, lithium carbonate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, lithium iodate, lithia, lithium peroxide, lithium sulfide, hydrogen lithium sulfide, lithium sulfate, lithium hydrogen sulfate, lithium nitride, Lithium Azide, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate and lithium bicarbonate; And organic compound, for example lithium methide, ethylidene lithium, isopropyl lithium, butyl lithium, phenyl lithium, lithium oxalate and lithium acetate.
After the calcining, in case of necessity, calomel mercurous chloride is broken by using, classification or the like, can regulate particle size.
Next, will the nonaqueous electrolyte battery that use according to the active material of cathode of an embodiment of the invention described above be described.
(5) the 5th of rechargeable nonaqueous electrolytic battery the embodiment
(5-1) structure of rechargeable nonaqueous electrolytic battery
Fig. 9 has shown the cross-sectional structure that uses the rechargeable nonaqueous electrolytic battery of the active material of cathode of the 5th embodiment according to the present invention.
Under fully charged state, this secondary cell has the open circuit voltage that for example every target and anode are not less than 4.25V and are not more than 4.65V.
This secondary cell is so-called cylindrical battery, and is being the electrode assemblie 520 that has coiling in the battery case 501 of hollow cylindrical substantially.In the electrode assemblie 520 of reeling, strip-shaped cathode 502 and ribbon anode 503 are reeled by barrier film 504.
The open end of battery case 501 becomes relief valve device 508 and the positive temperature coefficient element (PTC element) 509 that is connected with battery cover 507 and is formed at battery cover 507 inboards by means of pad 510 by volume.The inside of sealed cell shell 501.Battery cover 507 is by for example constituting with battery case 501 identical materials.Relief valve device 508 is electrically connected to battery cover 507 by positive temperature coefficient element 509.When because internal short-circuit or when causing the internal pressure of battery to become being not less than certain value from the heat of outside, at this moment disc 511 rollbacks are with the electrical connection between cut-out battery cover 507 and the rolled electrode assembly 520.When temperature raise, positive temperature coefficient element 509 prevented the heat of the abnormal amount that big electric current causes thus by the resistivity Control current of increase.Pad 510 is made of the insulating material that for example surface is covered with pitch.
The electrode assemblie 520 of reeling has for example center pin 512, around this center pin rolled electrode.Negative electrode 502 in the electrode assemblie 520 of reeling is connected with the cathode leg of being made by for example aluminium Al etc. 513, and anode 503 is connected with the anode tap of being made by for example nickel etc. 554.Be electrically connected to battery cover 507 by being welded to relief valve device 508 cathode legs 513, and anode tap 514 is electrically connected to battery case 501 by welding.
[negative electrode]
Figure 10 is the guide wire of alternative shape that shows the electrode assemblie 520 of coiling shown in Figure 9.As shown in figure 10, negative electrode 502 has the cathode mixture layer 502B on cathode current collector 502A that for example has an opposite respect to one another and the both sides that are formed on cathode current collector 502A.Cathode mixture layer 502B can be formed on cathode current collector 502A only in the zone of a side.Cathode current collector 502A is made of for example metal forming such as aluminium foil.Cathode mixture layer 502B comprises for example active material of cathode, and if desired, can comprise for example graphite and binding agent polyvinylidene fluoride for example of conductive agent.As active material of cathode, can use active material of cathode according to above-mentioned embodiment.
[anode]
As shown in figure 10, anode 503 has the anode collector 503A that for example has an opposite respect to one another and is formed on anode mixture layer 503B on the both sides of anode collector 503A.Anode mixture layer 503B can be formed on anode collector 503A only in the zone of a side.Anode collector 503A is made of as copper Cu paper tinsel for example metal forming.Anode mixture layer 503B comprises for example active material of positive electrode, and if desired, can comprise for example polyvinylidene fluoride of binding agent.
Active material of positive electrode comprises anode material, can absorb/discharge lithium Li (hereinafter, being sometimes referred to as " anode material that can absorb/discharge lithium Li ").The nitride that the example that can absorb/discharge the anode material of lithium Li can comprise material with carbon element, metallic compound, oxide, sulfide, lithium is Li N for example
3, the lithium metal, form the metal and the polymeric material of alloy with lithium.
The example of material with carbon element can comprise low graphited carbon, easy graphited carbon, graphite, RESEARCH OF PYROCARBON, coke, vitreous carbon, organic polymer compounds sintered body, carbon fiber and activated carbon.Wherein, coke can comprise pitch coke, needle coke and petroleum coke.Organic polymer compounds sintered body refer to by suitable temperature lower calcination polymeric material for example phenol plastics or furane resins make it the material that carbonization obtains, in these materials some are divided into low graphitized carbon or easy graphited carbon.The example of polymeric material can comprise polyacetylene and polypyrrole.
In can absorbing/discharge these anode materials of lithium Li, preferred charging and discharge voltage approach the charging of lithium metal and the material of discharge voltage.This is because the charging and the discharge voltage of anode 503 is low more, and battery is easy more to have higher energy density.Wherein, material with carbon element is preferred, because their crystal structure has only little variation when charging and discharge, therefore, can obtain good cycle characteristics and big charging and discharge capacity.Especially preferred graphite is because it can provide big electrochemical equivalent and high energy density.Low graphitized carbon also is preferred, because it can provide good cycle characteristics.
In addition, the anode material that can absorb/discharge lithium Li can comprise simple substance lithium metal, can form the metallic element and the semimetallic elements of alloy with lithium Li together, comprises the alloy and the compound of such element.These materials are preferred, because they can provide high-energy-density.Especially, more preferably they and material with carbon element are used together,, can obtain good cycle characteristics and high-energy-density because in this case.Except the alloy that comprises two kinds or more of metallic elements, alloy used herein also comprises the alloy that contains one or more metallic elements and one or more semimetallic elements.This alloy can be in following state: solid solution, eutectic crystal (eutectic mixture), intermetallic compound and composition thereof.
The example of metallic element and semimetallic elements can comprise tin Sn, plumbous Pb, aluminium Al, indium In, silicon Si, zinc Zn, antimony Sb, bismuth Bi, cadmium Cd, magnesium Mg, boron, gallium Ga, germanium Ge, arsenic As, silver-colored Ag, zirconium Zr, yttrium Y and hafnium Hf or the like.The example of above-mentioned alloy and compound can comprise having chemical formula: Ma
sMb
tLi
uMaterial and have chemical formula a: Ma
pMc
qMd
rMaterial.In these chemical formulas, Ma represents and can form the metallic element of alloy and at least a element in the semimetallic elements with lithium; Mb represents metallic element except that lithium and Ma and at least a element in the semimetallic elements; Mc represents at least a element in the nonmetalloid; Md represents metallic element except that Ma and at least a element in the semimetallic elements; And s, t, u, p, q and r satisfy s＞0, t 〉=0, u 〉=0, p＞0, q＞0 and r 〉=0.
Wherein, the metallic element and the semimetallic elements of preferred IVB family short period table, and the alloy and the compound that comprise such element, and preferred especially silicon Si, tin Sn and comprise Si and/or the alloy of Sn and compound.They can be crystal or unbodied.
In addition, can in negative electrode or anode, use the inorganic compound that does not comprise lithium Li, for example MnO
2, V
2O
5, V
6O
13, NiS and MoS.
[electrolyte solution]
As electrolyte solution, can use the non-aqueous electrolytic solution that obtains by dissolving electrolytic salt in non-water-soluble Ji.For example, preferred nonaqueous solvents can be for example to comprise solvent at least a in ethylene carbonate and the propylene carbonate, because they can improve cycle characteristics.Especially preferred is the mixture that comprises ethylene carbonate and propylene carbonate in electrolyte, because can further improve cycle characteristics.Comprise being selected from linear carbonate, for example the nonaqueous solvents of at least a ester in diethyl carbonate, dimethyl carbonate, the carbonic acid ethyl methyl esters also is preferred, and preferred carbonic acid first propyl ester, because they can further improve cycle characteristics.
Comprise 2, at least a nonaqueous solvents also is preferred in 4-difluoroanisole and the vinylene carbonate, because 2, the 4-difluoroanisole can improve discharge capacity, and vinylene carbonate can improve cycle characteristics.The nonaqueous solvents that more preferably comprises its mixture is because can improve discharge capacity and cycle characteristics.
Nonaqueous solvents can also comprise following at least a compound: butylene carbonate, gamma-butyrolacton, gamma-valerolactone, the compound that its (one or more) oh group is replaced in whole or in part by fluoro-containing group, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, 1, the 3-dioxolane, the 4-methyl isophthalic acid, the 3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxy-propyl nitrile, N, dinethylformamide, the N-methyl pyrrolidone, N-Jia Ji oxazolidine ester, N, N-methylimidazole alkane ketone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide (DMSO) and trimethyl phosphate.
In some cases, can improve the invertibity of electrode reaction by using the material that comprises in the above-mentioned nonaqueous solvents, according to will in conjunction with electrode, (one or more) hydroxyl of this material is replaced in whole or in part by fluorine atom.Can suitably use these materials.
Suitable example as the lithium salts of electrolytic salt can comprise LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiCl, LiBF
2(ox) difluoro lithium borate (oxalato), LiBOB and LiBr.They can use separately or can use its mixture.Wherein, LiPF
6Be preferred, because can obtain high ionic conductivity and can improve cycle characteristics.
[barrier film]
Now, will the diaphragm material that can use be described in first embodiment.As diaphragm material, can use the material that has been used for conventional batteries.In them, especially preferably use microporous polyolefin film, they have good effect to preventing short circuit, and can be by turn-offing the stability of effect improving battery.For example, the microporous barrier of preferably making by polyvinyl resin or acrylic resin.
As diaphragm material, from the viewpoint of well balanced turn-off performance and flotation property, also preferred the use has low polyacrylic duplexer or the mixture that turn-offs the polyethylene of temperature and have highly-acidproof.
(5-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, will method that make rechargeable nonaqueous electrolytic battery be described.To be that example is described this method with cylindrical rechargeable nonaqueous electrolytic battery.
Following manufacturing negative electrode 502.At first, for example active material of cathode, conductive agent and binding agent are mixed with the preparation cathode mix, then the cathode mix that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of cathode mix.
Subsequently, the slurry of cathode mix is coated on the cathode current collector 502A, and dry solvent, uses roll squeezer etc. to suppress moulding then, form cathode mixture layer 502B, negative electrode 502 is made of this cathode mixture layer.
Following manufacturing anode 503.At first, for example active material of positive electrode and binding agent are mixed with the preparation anode mixture, then the anode mixture that obtains is dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-, obtain the slurry of anode mixture.
Subsequently, the slurry of anode mixture is coated on the anode collector 503A, and dry solvent, uses roll squeezer etc. to suppress moulding then, form anode mixture layer 503B, anode 503 is made of this anode mixture layer.
Next, cathode leg 513 is connected to cathode current collector 502A by for example welding, and by the welding etc. anode tap 514 is connected to anode collector 503A.Then, by barrier film 504 coiling negative electrodes 502 and anode 503, and the leading section of cathode leg 513 is welded to relief valve device 508, the leading section with anode tap 514 is welded to battery case 501 simultaneously.Then, the negative electrode 502 and the anode 503 of reeling is clipped between a pair of insulation board 505 and 506, it is contained in the battery case 501.
Then, electrolyte solution is injected in the battery case 501, uses electrolyte solution impregnation barrier film 504 thus.Subsequently, with battery cover 507, relief valve device 508 and positive temperature coefficient element 509 by pad 510 at the open end crimping of battery case 501 so that they are fixed, thereby make rechargeable nonaqueous electrolytic battery.
(6) the 6th of rechargeable nonaqueous electrolytic battery the embodiment
(6-1) structure of rechargeable nonaqueous electrolytic battery
Figure 11 has shown the structure of using the rechargeable nonaqueous electrolytic battery of active material of cathode according to an embodiment of the invention.As shown in figure 11, rechargeable nonaqueous electrolytic battery has such structure, and wherein cell device 530 is contained in the clad material of being made by moistureproof stack membrane 537, and the periphery of welding cell device 530 is with sealing.Cell device 530 has cathode leg 532 and anode tap 533, and these lead-in wire encapsulated materials 537 are clipped in the middle and are drawn out to the outside.The both sides of cathode leg 532 and anode tap 533 are all covered by resin sheet 534 and resin sheet 535, so that improve the attachment characteristic to clad material 537.
[clad material]
[cell device]
Are coiling cell devices 530 by cell device shown in Figure 11 530 for example, it is stacked and reel at longitudinal direction wherein will to have ribbon anode 543, the barrier film 504 of the gel electrolyte layer 545 that is formed on its both sides, the strip-shaped cathode 542 with the gel electrolyte layer 545 that is formed on its both sides and a barrier film 504.
Negative electrode 542 is to be made of strip-shaped cathode collector 542A and the cathode mixture layer 542B that is formed on the cathode current collector 542A both sides.Cathode current collector 542A is the metal forming of being made by for example aluminium Al.
End at negative electrode 542 forms cathode leg 532 at longitudinal direction, and cathode leg 532 is connected to electrode by spot welding or ultra-sonic welded.As the material of cathode leg 532, can use for example metal of aluminium.
Anode 543 is to be made of ribbon anode collector 543A and the anode mixture layer 543B that be formed on the both sides of anode collector 543A.For example copper Cu paper tinsel, nickel foil or stainless steel foil constitute anode collector 543A by metal forming.
Be similar to negative electrode 542, form anode tap 533 at an end of anode 543 at longitudinal direction, it is connected to electrode by spot welding or ultra-sonic welded.Can use the material of the metal of copper Cu for example or nickel as anode tap 533.
Because identical in parts except that gel electrolyte layer 545 and first embodiment, so below gel electrolyte layer 545 will be described.
The example of polymer compound can comprise copolymer, polytetrafluoroethylene, polyhexafluoropropylene, poly(ethylene oxide), PPOX, poly phosphazene, polysiloxanes, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, acrylonitrile-butadiene rubber, polystyrene and the Merlon of polyacrylonitrile, polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene.From the viewpoint of electrochemical stability, special optimization polypropylene nitrile, polyvinylidene fluoride, polyhexafluoropropylene and poly(ethylene oxide).
(6-2) method of manufacturing rechargeable nonaqueous electrolytic battery
Next, make the method for rechargeable nonaqueous electrolytic battery with describing the active material of cathode that uses according to an embodiment of the invention.At first,, evaporate mixed solvent then, to form gel electrolyte layer 545 with comprising the precursor solution coated cathode 542 of solvent, electrolytic salt, polymer compound and mixed solvent and each of anode 543.By welding the end that cathode leg 532 is connected in advance cathode current collector, simultaneously, also anode tap 533 is connected to the end of anode collector 543A by welding.
Subsequently, by barrier film 544 that negative electrode 542 and anode 543 is stacked, all formed gel electrolyte layer 545 on negative electrode 542 and the anode 543, and the laminated body that obtains has been reeled at longitudinal direction, to form coiling cell device 530.
Next, the clad material 537 that is made of stack membrane is drawn forming recessed portion 536, and cell device 530 is incorporated in the recessed portion 536.Then the unprocessed portion of clad material 537 is bent to the top of recessed portion 536, the periphery that welds recessed portion 536 is then made rechargeable nonaqueous electrolytic battery thus with sealing.
[embodiment]
To describe according to embodiment of the present invention by means of embodiment, but the present invention is not limited to this.
＜embodiment 9 〉
At first, by stirring 1 hour down at 80 ℃, 20 weight portion composite oxide particles are dispersed in the pure water of 300 weight portions, this composite oxide particle has average composition Li
1.03CoO
2.01Average particle size particle size with the 13 μ m that measure by laser scattering method.
Subsequently, add the commercial reagents nitric acid nickel (NO of 1.60 weight portions to this dispersion
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 1.65 weight portions
3)
26H
2O, and in 30 minutes to wherein adding the 2N LiOH aqueous solution, so that pH is adjusted to 13.Continue to stir this dispersion down at 80 ℃ and continue other 3 hours, afterwards with its cooling.
Next, clean this dispersion, the commercial reagents ammonium metavanadate NH in the pure water that is dissolved in 30.0 weight portions that wherein adds 0.1 weight portion by decant
4VO
3Then,, filter at last by the decant washed mixture, and at 120 ℃ of following dry filter things to form precursor.
Then, in order to regulate the amount of lithium, flood the gained precursor sample of 10 weight portions, mix this precursor sample equably, and dry this mixture obtains the precursor that is used to calcine with the 2N LiOH aqueous solution of 2 weight portions.The temperature that flows down the precursor that the speed with 5 ℃ of per minutes will be used to calcine at air in electric furnace is elevated to 950 ℃.Kept 5 hours under this temperature, the speed with 7 ℃ of per minutes is cooled to 150 ℃ then, obtains the active material of cathode of embodiment 9.
＜embodiment 10 〉
At first, under 80 ℃, by stir with 20 weight portions with embodiment 9 in identical composite oxide particle be dispersed in the 2N LiOH aqueous solution of 300 weight portions 2 hours (this system has 14.2 pH).Subsequently, by pure water being added to the commercial reagents nitric acid nickel (NO of 1.60 weight portions
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 1.65 weight portions
3)
26H
2The aqueous solution for preparing 10 weight portions among the O.And in 2 hours with in the dispersion that all aqueous solution of 10 weight portions of amount obtains above adding to, and continue to stir this dispersion down at 80 ℃ and continue other 1 hour, cooling subsequently.
Next, clean this dispersion, the commercial reagents sodium metavanadate NaVO in the pure water that is dissolved in 20.0 weight portions that wherein adds 0.2 weight portion by decant
3Then,, filter at last by the decant washed mixture, and at 120 ℃ of following dry filter things to form precursor.In electric furnace, flow down with the speed of 5 ℃ of per minutes the temperature of the precursor that obtains is elevated to 950 ℃ at air.Under this temperature it was kept 5 hours, the speed with 7 ℃ of per minutes is cooled to 150 ℃ then, thereby obtains the active material of cathode of embodiment 10.
＜embodiment 11 〉
Make the active material of cathode of embodiment 11 in the mode identical with embodiment 10, difference is by pure water being added to the commercial reagents nitric acid nickel (NO of 3.20 weight portions
3)
26H
2The commercial reagents manganese nitrate Mn (NO of O and 3.30 weight portions
3)
26H
2The aqueous solution for preparing 20 weight portions among the O, and in 3 hours, add all aqueous solution of 20 weight portions of amount; And with the commercial reagents ammonium metavanadate NH of 0.2 weight portion
4VO
3Be dissolved in the pure water of 50.0 weight portions, and add the aqueous solution that obtains.
＜comparative example 5 〉
The same compound oxide particle that uses among use and the embodiment 9 is 5 active material of cathode as a comparative example, and this composite oxide particle has average composition Li
1.03CoO
2.01Average particle size particle size with the 13 μ m that measure by laser scattering method.
＜comparative example 6 〉
Remove the ammonium metavanadate NH that does not add 0.1 weight portion
4VO
3Outside make the active material of cathode of comparative example 6 in the mode identical with embodiment 9.
Measure:
Use the active material of cathode of making in embodiment 9 to 11 and comparative example 5 and 6, the secondary cell shown in the shop drawings 9 and 10.At first, that mixes 86wt% makes cathode active material powder, 10wt% as the graphite of conductive agent and the 4wt% polyvinylidene fluoride as binding agent, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP).Then, this dispersion is coated on the cathode current collector 502A both sides that are made of the thick banded aluminium foil of 20 μ m, and with the collector drying that obtains.Suppress moulding by the use roll squeezer subsequently, thereby form cathode mixture layer 502B, make negative electrode 502 thus.At this moment, thoroughly pulverize this cathode active material powder, so that pass filter screen with 70 μ m apertures with kneading machine.The porosity of cathode mixture layer 502B is controlled to be 26% volume ratio.Next, aluminium cathode leg 513 is connected to cathode current collector 502A.
Individually, 90wt% is mixed as the polyvinylidene fluoride of binding agent as the Delanium powder of active material of positive electrode and 10wt%, and this mixture is dispersed in the solvent N-N-methyl-2-2-pyrrolidone N-.Then, with this minute dispersion be coated on the anode collector 503A both sides that constitute by the thick banded Copper Foil of 10 μ m, and with the collector drying that obtains.Use roll squeezer to suppress moulding subsequently, thereby form anode mixture layer 503B, make anode 503 thus.Next, nickel cathode lead-in wire 514 is connected to anode collector 503A.
The strip-shaped cathode 502 and the ribbon anode 503 that obtain are thus much enclosed by reeling as the porous polyolefin membrane of barrier film 544, so that make the electrode assemblie 520 of screw winding.The electrode assemblie 520 of reeling is contained in the battery case 501 of irony, and a pair of insulation board 505 and 506 is placed on the top side and bottom side of rolled electrode assembly 520.Then, cathode leg 513 is guided to the outside of cathode current collector 502A, and be welded to relief valve device 508.Similarly, anode tap 514 is guided to anode collector 503A outside, and be welded to the bottom of battery case 501.Thereafter, electrolyte solution is injected into the inside of battery case 501, and carry out crimping by 510 pairs of battery cases of pad 501, with fixedly relief valve device 508, positive temperature coefficient element 509 and battery cover 507, obtain to have the column secondary battery of 18mm overall diameter and 65mm height thus.As electrolyte solution, use electrolytic salt LiPF by dissolving 1.0mol/l in the solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1)
6The solution that obtains.
The secondary cell of so making is charged under 45 ℃ of temperature and discharge, determine initial capacity and discharge capacitance thus, this initial capacity is the discharge capacity of the circulation time first time, and this discharge capacitance is the ratio in discharge capacity with the circulation time discharge capacity first time of the 200th circulation.
Carry out constant current charge by constant current and reach 4.40V, carry out constant voltage charge with the constant voltage of 4.40V then and reach 2.5 hours up to total charging interval and carry out charging up to cell voltage with 1000mA.Carrying out constant-current discharge by the constant current with 800mA reaches 2.75V up to cell voltage and carries out discharge.In measurement result shown in the table 3.
[table 3]
| Initial capacity (mAh) | Discharge capacitance (%) | |
| Embodiment 9 | 2440 | 83 |
| Embodiment 10 | 2430 | 85 |
| Embodiment 11 | 2440 | 86 |
| Comparative example 5 | 2440 | 34 |
| Comparative example 6 | 2450 | 81 |
As shown in table 3, should be understood that the battery of the active material of cathode that use obtains has the higher discharge capacitance of battery of the active material of cathode that obtains in high capacity and the ratio use comparative example 5 and 6 in embodiment 9 to 11.
The present invention is not limited to above-mentioned embodiment of the present invention, can make various deformation and application under the condition that does not break away from the scope of the invention.For example, its shape is restriction especially not, can use cylindrical shape type, square type, Coin shape, button type or the like.
In the 5th embodiment, rechargeable nonaqueous electrolytic battery with electrolyte solution as electrolyte, and in the 6th embodiment, rechargeable nonaqueous electrolytic battery with gel electrolyte as electrolyte.Yet the present invention is not limited to this.
For example, not only can use above-mentioned electrolyte, but also can use the copolymer solid electrolyte that utilizes ionic conduction polymer, the inorganic solid electrolyte of utilizing the ionic conduction inorganic material is as electrolyte.And they can use separately or conduct is used with the electrolytical mixture of another kind.The example that is used for the polymer of solid polyelectrolyte can comprise polyethers, polyester, polyphosphazene and polysiloxanes.The example of inorganic solid electrolyte can comprise ionic conductivity ceramics, ionic conduction transistor and ionic conducting glass.
In addition, for example, the electrolyte solution in the rechargeable nonaqueous electrolytic battery is not particularly limited, and can use electrolyte solution of conventional non-aqueous solvent system or the like.Wherein, the preferred example of the non-aqueous electrolytic solution that comprises alkali metal salt in the secondary cell comprises propylene carbonate, ethylene carbonate, gamma-butyrolacton, N-methyl pyrrolidone, acetonitrile, N, dinethylformamide, methyl-sulfoxide, oxolane, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxy-ethane, carbonic acid two ethyls, its derivative and composition thereof.The electrolytical preferred example that comprises in the electrolyte solution comprises alkali metal, especially calcium halide, perchlorate, rhodanate, borofluoride, fluorophosphate, fluoridize arsenic, yttrium fluoride and trifluoromethyl sulfate.
Claims (41)
1. active material of cathode comprises:
Coat, this coat are formed at least a portion of composite oxide particle and comprise and contain lithium Li oxide and contain the oxide that applies element nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise molybdenum Mo, wherein
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
2. according to the active material of cathode of claim 1, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 99: 1 to 30: 70 scope.
3. according to the active material of cathode of claim 1, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
4. according to the active material of cathode of claim 1, wherein based on composite oxide particle, the amount of coat is in 0.5wt% arrives the scope of 50wt%.
5. according to the active material of cathode of claim 1, it has the average particle size particle size of 2.0 μ m to 50 μ m.
6. a method of making active material of cathode comprises the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises the hydroxide that contains nickel or nickel and manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, and then molybdic acid is administered at least a portion of composite oxide particle; And
Use after the molybdic acid, the composite oxide particle that heating obtains, so that at least a portion of composite oxide particle, form coat, this coat comprises and contains lithium Li oxide and contain the oxide that applies element nickel or nickel and manganese Mn, and at least a portion of coat, form superficial layer, and this superficial layer comprises molybdenum Mo
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
7. according to the method for the manufacturing active material of cathode of claim 6, wherein by disperseing composite oxide particle mainly comprising water and have in the solution that is not less than 12 pH, then nickel compound or nickel compound and manganese Mn compound are added to wherein, form the hydroxide that contains nickel or nickel and manganese Mn.
8. according to the method for the manufacturing active material of cathode of claim 7, the solution that wherein mainly comprises water comprises lithium hydroxide.
9. according to the method for the manufacturing active material of cathode of claim 6, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 99: 1 to 30: 70 scope.
10. according to the method for the manufacturing active material of cathode of claim 6, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
11. according to the method for the manufacturing active material of cathode of claim 6, wherein based on composite oxide particle, the amount of coat at 0.5wt% in the scope of 50wt%.
12. according to the method for the manufacturing active material of cathode of claim 6, wherein active material of cathode has the average particle size particle size of 2.0 μ m to 50 μ m.
13. a rechargeable nonaqueous electrolytic battery comprises
Negative electrode with active material of cathode;
Anode;
Barrier film; With
Electrolyte, wherein
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise the oxide that contains lithium Li oxide and contain at least a coating element of nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise molybdenum Mo, and
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
14. an active material of cathode comprises:
Coat, this coat are formed at least a portion of composite oxide particle and comprise the oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise yttrium Y, wherein
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
15. according to the active material of cathode of claim 14, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 100: 0 to 30: 70 scope.
16. active material of cathode according to claim 14, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
17. active material of cathode according to claim 14, wherein with the yttrium Y in the oxide that is selected from least a metallic element substitution tables surface layer among magnesium Mg, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, aluminium Al, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W and the zirconium Zr, alternative amount is no more than the 20mol% of the yttrium Y total amount in the oxide in the superficial layer.
18. want 14 active material of cathode according to right, wherein based on the composite oxide particle of 100 weight portions, the amount of coat is that 0.5 weight portion is to 50 weight portions.
19. according to the active material of cathode of claim 14, it has the average particle size particle size of 2.0 μ m to 50 μ m.
20. a method of making active material of cathode comprises the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises the hydroxide that contains nickel and/or manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, forms the hydroxide that contains yttrium Y then at least a portion of composite oxide particle; And
The composite oxide particle that heating obtains after formation contains the hydroxide of yttrium Y, so that at least a portion of composite oxide particle, form coat, this coat comprises the oxide that contains lithium Li oxide and contain at least a coating element among nickel and the manganese Mn, and at least a portion of coat, form superficial layer, and this superficial layer comprises yttrium Y
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
21. method according to the manufacturing active material of cathode of claim 20, wherein by disperseing composite oxide particle mainly comprising water and have in the solution that is not less than 12 pH, and then nickel compound and/or manganese Mn compound are added to wherein, form the hydroxide that contains nickel and/or manganese Mn.
22. according to the method for the manufacturing active material of cathode of claim 21, the solution that wherein mainly comprises water comprises lithium hydroxide.
23. according to the method for the manufacturing active material of cathode of claim 20, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 100: 0 to 30: 70 scope.
24. method according to the manufacturing active material of cathode of claim 20, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and the zirconium Zr, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
25. method according to the manufacturing active material of cathode of claim 20, wherein with the yttrium Y in the oxide that is selected from least a metallic element substitution tables surface layer among magnesium Mg, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, aluminium Al, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W and the zirconium Zr, alternative amount is no more than the 20mol% of the yttrium Y total amount in the oxide in the superficial layer.
26. according to the method for the manufacturing active material of cathode of claim 20, wherein based on the composite oxide particle of 100 weight portions, the amount of coat at 0.5 weight portion in the scope of 50 weight portions.
27. according to the method for the manufacturing active material of cathode of claim 20, wherein active material of cathode has the average particle size particle size of 2.0 μ m to 50 μ m.
28. a rechargeable nonaqueous electrolytic battery comprises
Negative electrode:
Anode:
Barrier film; With
Electrolyte; Wherein
This negative electrode has active material of cathode,
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise the oxide that contains lithium Li oxide and contain at least a coating element of nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise and contain yttrium Y oxide, and
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn, calcium Ca, strontium Sr, tungsten W, yttrium Y and zirconium Zr; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
29. an active material of cathode comprises:
Coat, this coat are formed at least a portion of composite oxide particle and comprise the oxide that contains lithium Li oxide and contain the coating element of nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise vanadium V, wherein
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
30. according to the active material of cathode of claim 29, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 100: 0 to 30: 70 scope.
31. active material of cathode according to claim 29, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
32. according to the active material of cathode of claim 29, wherein based on composite oxide particle, the amount of coat is in 0.5wt% arrives the scope of 50wt%.
33. according to the active material of cathode of claim 29, it has the average particle size particle size of 2.0 μ m to 50 μ m.
34. a method of making active material of cathode comprises the steps:
Cambium layer at least a portion of composite oxide particle, this layer comprises the hydroxide that contains nickel or nickel and manganese Mn, this composite oxide particle has average composition the by following formula 1 expression, and applies vanadic acid then at least a portion of composite oxide particle; And
The composite oxide particle that heating obtains after applying vanadic acid, so that at least a portion of composite oxides, form coat, this coat comprises and contains lithium Li oxide and contain the oxide that applies element nickel or nickel and manganese Mn, and at least a portion of coat, form superficial layer, and this superficial layer comprises vanadium V
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is at least a element that is selected among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
35. method according to the manufacturing active material of cathode of claim 34, wherein by disperseing composite oxide particle mainly comprising water and have in the solution that is not less than 12 pH, and then nickel compound or nickel compound and manganese Mn compound are added to wherein, form the hydroxide that contains nickel or nickel and manganese Mn.
36. according to the method for the manufacturing active material of cathode of claim 35, the solution that wherein mainly comprises water comprises lithium hydroxide.
37. according to the method for the manufacturing active material of cathode of claim 34, wherein in the coat constitutive molar ratio example of nickel and manganese Mn in 100: 0 to 30: 70 scope.
38. method according to the manufacturing active material of cathode of claim 34, wherein substitute nickel and manganese Mn in the oxide in the coat with being selected from least a metallic element among magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, iron Fe, cobalt Co, copper Cu, zinc Zn, molybdenum Mo, tin Sn and the tungsten W, alternative amount is no more than the 40mol% of nickel and manganese Mn total amount in the oxide in the coat.
39. according to the method for the manufacturing active material of cathode of claim 34, wherein based on composite oxide particle, the amount of coat at 0.5wt% in the scope of 50wt%.
40. according to the method for the manufacturing active material of cathode of claim 34, wherein active material of cathode has the average particle size particle size of 2.0 μ m to 50 μ m.
41. a rechargeable nonaqueous electrolytic battery comprises:
Negative electrode with active material of cathode;
Anode;
Barrier film; With
Electrolyte, wherein
This active material of cathode comprises
Coat, this coat are formed at least a portion of composite oxide particle and comprise and contain lithium Li oxide and contain the oxide that applies element nickel or nickel and manganese Mn; And
Superficial layer, this superficial layer are formed at least a portion of coat and comprise vanadium V, and
This composite oxide particle has average composition the by formula 1 expression,
(formula 1)
Li
(1+x)Co
(1-y)M
yO
(2-z)
Wherein M is magnesium Mg, aluminium Al, boron, titanium Ti, vanadium V, chromium Cr, manganese Mn, iron Fe, nickel, copper Cu, zinc Zn, molybdenum Mo, tin Sn and tungsten W; And x, y and z satisfy-0.10≤x≤0.10,0≤y＜0.50 and-relation of 0.10≤z≤0.20.
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| WO2013154142A1 (en) * | 2012-04-11 | 2013-10-17 | 旭硝子株式会社 | Positive electrode active material for lithium-ion secondary cell |
| US11081731B2 (en) * | 2017-10-18 | 2021-08-03 | International Business Machines Corporation | High-capacity rechargeable batteries |
| CN109509875B (en) * | 2018-11-26 | 2021-09-10 | 合肥国轩高科动力能源有限公司 | High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
| US20200259232A1 (en) * | 2019-02-13 | 2020-08-13 | Ec Power, Llc | Stable battery with high performance on demand |
| GB202002417D0 (en) * | 2020-02-21 | 2020-04-08 | Johnson Matthey Plc | Process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319905A (en) * | 2000-03-24 | 2001-10-31 | 默克专利股份有限公司 | Lithium mixed oxide coated grain and preparation method |
| CN1350706A (en) * | 1999-05-15 | 2002-05-22 | 默克专利股份有限公司 | Lithium-mixed oxide particles coated with metal-oxides |
| CN1731605A (en) * | 2005-07-27 | 2006-02-08 | 浙江大学 | Surface modification modified lithium ion battery positive electrode material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09293508A (en) * | 1996-04-25 | 1997-11-11 | Sony Corp | Positive electrode material for lithium secondary battery, its manufacture and nonaqueous electrolyte secondary battery using it |
| JP2000195517A (en) * | 1998-12-28 | 2000-07-14 | Japan Storage Battery Co Ltd | Lithium secondary battery |
| KR100309769B1 (en) * | 1999-06-17 | 2001-11-01 | 김순택 | Positive active material for lithium secondary battery and method of preparing the same |
| KR100428616B1 (en) * | 2001-01-19 | 2004-04-27 | 삼성에스디아이 주식회사 | Positive active material for lithium secondary battery and method of preparing same |
| KR100508941B1 (en) * | 2003-11-29 | 2005-08-17 | 삼성에스디아이 주식회사 | Method of preparing positive active material for rechargeable lithium battery and positive active material for rechargeable lithium battery fabricated using same |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350706A (en) * | 1999-05-15 | 2002-05-22 | 默克专利股份有限公司 | Lithium-mixed oxide particles coated with metal-oxides |
| CN1319905A (en) * | 2000-03-24 | 2001-10-31 | 默克专利股份有限公司 | Lithium mixed oxide coated grain and preparation method |
| CN1731605A (en) * | 2005-07-27 | 2006-02-08 | 浙江大学 | Surface modification modified lithium ion battery positive electrode material and preparation method thereof |
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| CN101098027A (en) | 2008-01-02 |
| JP2007242284A (en) | 2007-09-20 |
| CN101662016B (en) | 2012-10-10 |
| CN101662016A (en) | 2010-03-03 |
| JP5076332B2 (en) | 2012-11-21 |
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