CN1294665C - Anode active material for non-aqueous secondary cell, and its preparing method and non-aqueous secondary cell using same - Google Patents
Anode active material for non-aqueous secondary cell, and its preparing method and non-aqueous secondary cell using same Download PDFInfo
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- CN1294665C CN1294665C CNB03140216XA CN03140216A CN1294665C CN 1294665 C CN1294665 C CN 1294665C CN B03140216X A CNB03140216X A CN B03140216XA CN 03140216 A CN03140216 A CN 03140216A CN 1294665 C CN1294665 C CN 1294665C
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- positive electrode
- aqueous secondary
- electrode active
- lithium
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- 238000000034 method Methods 0.000 title claims description 21
- 239000006183 anode active material Substances 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 22
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 6
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MXEHMOBFYMIGAE-UHFFFAOYSA-L cobalt(2+);nickel;dihydroxide Chemical compound [OH-].[OH-].[Co+2].[Ni] MXEHMOBFYMIGAE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011163 secondary particle Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000001788 irregular Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- -1 lithium nickel cobalt metal oxides Chemical class 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NONOLKTXYXUTHP-UHFFFAOYSA-L O[Ni](O)=O Chemical compound O[Ni](O)=O NONOLKTXYXUTHP-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/52—Solid solutions containing elements as dopants
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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Abstract
The present invention relates to a positive pole active material of a nonaqueous secondary battery, a preparation method thereof and a nonaqueous secondary battery using the positive pole active material. A molecular formula of the positive pole active material is Li <a> Ni<1-b-c> Co<b> M<c> O2 (the a is more than or equal to 0.97 and is less than or equal to 1.05, the b is more than or equal to 0.01 and is less than or equal to 0.03, the c is more than or equal to 0 and is less than or equal to 0.10 and the M is one kind of or several kinds of Mn, Al, Ti, Cr, Mg, Ca, V, Fe and Zr.). The positive pole active material is formed from small crystal particles of which the volume content is less than or equal to 10% and the average particle diameter is from 0.5 to 4 mum and secondary particles of which the average particle diameter is from 10 to 40 mum. Spherical high-cobalt nickel hydroxide (Ni <1-b> Co<b> OH2) and a lithium compound are roasted to prepare the positive pole active material. The positive pole active material of a nonaqueous secondary battery has high tap density. The nonaqueous secondary battery using the positive pole active material has the advantages of excellent discharge capacity, excellent cycle performance and excellent multiplying power current discharge performance.
Description
[technical field]
The non-aqueous secondary batteries that the present invention relates to a kind of non-aqueous secondary batteries positive electrode active materials, its manufacture method and use this material.
[background technology]
In recent years, along with being extensive use of of various portable type electronic products, lithium rechargeable battery with its many superior performance such as voltage height, specific energy is big, self discharge is little and memory-less effect etc. enjoys favor.Wherein, the positive electrode that lithium battery uses mainly is an intercalation compounds, and the best positive electrode of combination property is cobalt acid lithium LiCoO at present
2Material.
But LiCoO
2The costing an arm and a leg and originate shortage of material.Therefore, as LiCoO
2The substitute of material, people advise using lithium manganese oxide or lithium nickel oxide.For overcoming some defectives that lithium manganese oxide and lithium nickel oxide self exists, generally need mix or coat processing it.At present, lithium nickel oxide is carried out the LiNi that cobalt mixes and obtains
1-bCo
bO
2Material becomes the focus of people's research.
At preparation LiNi
1-bCo
bO
2During material, people generally adopt mixed lithiated compound, nickel compound and cobalt compound to carry out the method for high-temperature roasting.
At Chen.Express, in 6,161191 documents, provided a kind of LiNi
1-bCo
bO
2The manufacture method of material: with Ni (NO
3)
2, Co (NO
3)
2Be mixed together with the solution of LiOH, elder generation is with this mixture preliminarily dried down at 90 ℃ then, and heat treatment in 800 ℃ air again makes product thus.
A kind of LiNi is disclosed among the flat 2000-058053 of day present disclosure specification
1-bCo
bO
2The synthetic method of material: mix lithium salts, cobalt salt and nickel salt by a certain percentage, under 300～700 ℃, roasting was ground more than 2 hours in the dry no carbon dioxide air atmosphere, more than 700～900 ℃ of roasting 2h, obtained the material that needs again.
In addition, because Ni
3+Ion is reduced into Ni easily under higher temperature
2+Ion, people adopt again earlier Ni
2+Ion-oxygen changes into Ni
3+Ion, the method for roasting reactant mixture prepares LiNi at a lower temperature again
1-bCo
bO
2Material.
In Chinese publication CN1142691A, provided oxygen-nickel hydroxide Ni that a kind of use contains cobalt
1-yCo
yOOH and a kind of lithium compound are raw material, and the method for heat-treating under 400～500 ℃ prepares LiNi
1-bCo
bO
2Material.
LiNi
1-bCo
bO
2Material is six side's layer structures, and in building-up process, the growth on the C direction of principal axis forms the lath body, thereby obtains crystal in irregular shape easily.For guaranteeing conductance, this crystal in irregular shape needs to add conductive agent in use, is difficult to improve packed density, otherwise discharge capacity and multiplying power current discharge properties will be relatively poor.In addition, synthetic methods more above-mentioned need to grind when handling product, can produce the particle of meticulous pulverizing, have increased the specific area of material, for conductance is provided, just must add a large amount of conductive agents.
Therefore, be used for synthetic LiNi above
1-bCo
bO
2In the method for material, except owing to existing crystallization degree to reduce the specific capacity of positive electrode inadequately, be unfavorable for that also thereby the packed density that improves material improves the volume and capacity ratio of material or the anodal volume and capacity ratio decline that the too much conductive agent of needs adding causes secondary cell, and heavy-current discharge performance is relatively poor.
[summary of the invention]
The non-aqueous secondary batteries that the purpose of this invention is to provide a kind of non-aqueous secondary batteries positive electrode active materials and preparation method thereof and use this positive electrode with bigger ram-jolt density.This non-aqueous secondary batteries has good discharge capacity, cycle performance and multiplying power current discharge properties.
The objective of the invention is to be achieved through the following technical solutions:
A kind of non-aqueous secondary batteries positive electrode active materials, (1) are Li with the chemical formulation
aNi
1-b-cCo
bM
cO
2(0.97≤a≤1.05,0.01≤b≤0.30,0≤c≤0.10, M is one or more among Mn, Al, Ti, Cr, Mg, Ca, V, Fe and the Zr); (2) this positive electrode active materials is made of the second particle that small crystals particle and small crystals particle aggregation form, and wherein the small crystals grain diameter is 0.5～4 μ m, and the second particle particle diameter is 10～40 μ m, and small crystals particle volume≤cumulative volume 10%.
Further described second particle is to be mutually combined by the small crystals particle in sintering process and constantly increase the Li that grows up and form
aNi
1-b-cCo
bM
cO
2Crystal grain is shaped as sphere or elliposoidal.
A kind of above-mentioned non-aqueous secondary batteries manufacture method of positive electrode active materials, it comprises the steps:
(1) preparation of high cobalt nickel hydroxide: adopt in cobaltous sulfate that mixes and nickel sulfate solution
Add ammoniacal liquor and prepare high cobalt nickel hydroxide, its structure can be expressed as
Ni
1-bCo
b(OH)
2, 0.01≤b≤0.30 wherein;
(2) lithium nickel cobalt composite oxide of metal Li
aNi
1-b-cCo
bM
cO
2Preparation:
A. first section roasting: get lithium compound and above-mentioned Ni
1-bCo
b(OH)
2, the M compound mixed in the ratio ball milling of Li/ (Ni+Co+M) between 1.01～1.10, the roasting temperature under the oxygen atmosphere, between 600 ℃ to 720 ℃ 1～10 hour;
B. second section roasting: with the product of step a again the roasting temperature under the oxygen atmosphere, between 750 ℃ to 900 ℃ 8～20 hours;
C. step b products therefrom quenching, ball milling, screening can be obtained described non-aqueous secondary batteries positive electrode active materials.
The high cobalt hydroxide nickel of control in step (1)
1-bCo
b(OH)
2Be shaped as sphere or elliposoidal, control its average grain diameter D
50〉=8 μ m, D
10〉=4 μ m, D
90≤ 30 μ m.Wherein: the shape of high cobalt nickel hydroxide is observed by the SEM scanning analysis; Particle diameter D
50, D
10, D
90Be respectively the D that measures with the laser light scattering particle size analyzer
50, D
10, D
90
In order to remedy the volatilization of lithium in the high-temperature calcination process, must increase the consumption of lithium compound in right amount, therefore in reactant ratio, should guarantee that Li/ (Ni+Co+M) is between 1.01～1.10.
Restriction Li
aNi
1-b-cCo
bM
cO
2B value in the structure otherwise be the specific discharge capacity that affiliation reduces the lithium-nickel-cobalt-oxygen thing that obtains that adds of too much cobalt greater than 0.3 reason.
Lithium nickel cobalt composite oxide of metal (second particle) average grain diameter for preparing is that when particle diameter was too small, a part of powder can not contact with conductive agent, for guaranteeing conductance, must increase the consumption of conductive agent in the reason of 10～40 μ m; On the contrary, when its average grain diameter surpassed 40 μ m, electrolyte can not infiltrate and be penetrated into granule interior, causes the part of material can not fully be used to discharge and recharge reaction.
The lithium nickel cobalt composite oxide of metal for preparing is the ram-jolt density that can provide enough for the reason of sphere or elliposoidal, and other uncertain shape is unfavorable for the multiplying power current discharge properties of active material.
A kind of non-aqueous secondary batteries comprises following element:
(1) negative pole comprises among the material that can embed and separate out lithium ion, lithium metal, the lithium alloy one or more;
(2) positive pole comprises as any positive electrode active materials in claim 1 or 2;
(3) electrolyte contacts with anodal with described negative pole.
The invention has the advantages that: according to the present invention, by the Li that adopts proper raw material, control synthesis condition to obtain with small crystals particle and second particle structure
aNi
1-b-cCo
bM
cO
2Material has bigger ram-jolt density, demonstrates the chemical property of excellence as the positive electrode active materials of non-aqueous secondary batteries; Use the battery of this positive electrode to have good discharge capacity, cycle performance and multiplying power current discharge properties.
The present invention is further illustrated in conjunction with example with reference to the accompanying drawings.
[description of drawings]
Fig. 1 is that high cobalt nickel hydroxide amplifies 2000 times scanning electron microscope image.
Fig. 2 is that embodiment 4 product lithium nickel cobalt metal oxides amplify 2000 times scanning electron microscope image.
Fig. 3 is that embodiment 4 product lithium nickel cobalt metal oxides amplify 10000 times scanning electron microscope image.
Fig. 4 is an embodiment of the invention button cell profile.
[embodiment]
The invention provides a kind of non-aqueous secondary batteries positive electrode active materials, is Li with the chemical formulation
aNi
1-b-cCo
bM
cO
2(0.97≤a≤1.05,0.01≤b≤0.30,0≤c≤0.10, M is one or more among Mn, Al, Ti, Cr, Mg, Ca, V, Fe and the Zr); This positive electrode active materials is made of the second particle that small crystals particle and small crystals particle aggregation form, and wherein the small crystals grain diameter is 0.5～4 μ m, and the second particle particle diameter is 10～40 μ m, and small crystals particle volume≤cumulative volume 10%.The non-aqueous secondary batteries that the present invention also provides the preparation method of above-mentioned positive electrode active materials and used this material.
In order to obtain metal ion positive electrode arranged in a uniform, the arrangement again in the synthetic reaction of minimizing Ni and Co, the present invention's employing add ammoniacal liquor and prepare high cobalt nickel hydroxide in cobaltous sulfate that mixes and nickel sulfate solution, and its structure can be expressed as Ni
1-bCo
b(OH)
2Use the benefit of high cobalt nickel hydroxide to be, high cobalt nickel hydroxide can be prepared into sphere or elliposoidal (as shown in Figure 1), at Li
aNi
1-b-cCo
bM
cO
2Do not need to destroy this sphere in the material preparation process, but grow a lot of small crystalss (as shown in Figure 2), thereby can obtain the positive electrode active materials of sphere or elliposoidal, like this as long as particle diameter and form that particle diameter by controlling high cobalt nickel hydroxide and form just can be controlled material requested.
The lithium compound that uses in the reaction can be lithium compounds such as lithium hydroxide, lithia, lithium peroxide, lithium carbonate, lithium nitrate, from cost consideration, generally uses lithium carbonate.
High cobalt nickel hydroxide, lithium compound is prepared by a certain percentage and mix, and at high temperature divides two sections to carry out roast.At first carry out first section roasting under the temperature between 600 ℃ to 720 ℃, roasting time is 1～10 hour, carries out the decomposition and the Ni of high cobalt nickel hydroxide
2+The oxidizing process of ion; Carry out second section roasting again under the temperature between 750 ℃ to 900 ℃, roasting time is 8～20 hours, carries out the formation of small crystals particle and second particle: at first, the lithium ion that lithium compound decomposes enters into high cobalt nickel hydroxide ball inside, grows into a lot of Li
aNi
1-b-cCo
bM
cO
2Small crystals particle (both primary particle, its average grain diameter is 0.5～4 μ m), these small crystals particles are body with high cobalt nickel hydroxide ball, portion mutually combines and constantly increases to grow up and forms Li within it
aNi
1-b-cCo
bM
cO
2(its average grain diameter is 10～40 μ m to subgrain, as shown in Figure 3).If temperature is lower than 750 ℃ or time and is less than 8 hours in second section roasting process, then little grain growth can't be finished; If temperature surpasses 900 ℃ or time and surpasses 20 hours, then little grain growth is excessive, and extruding can't be combined together to form second particle mutually.For positive electrode for battery active material Li
aNi
1-b-cCo
bM
cO
2Second particle The more the better, and the small crystals particle is few more good more.In the reality, can obtain 10% of small crystals particle volume≤cumulative volume.When this positive electrode active materials is carried out particle size distribution test (with the Honeywell Microtarc X100 tester of the U.S.), D10 〉=6 μ m, the small crystals particle volume that does not promptly form second particle in this system is no more than 10% of cumulative volume.
Because Ni
3+Ion can be reduced into Ni again when temperature is higher than more than 600 ℃
2+Therefore ion needs the oxygen atmosphere to suppress the carrying out of this reaction.According to experiment, roasting process should be about under the atmospheric condition in partial pressure of oxygen and carries out.
When the preparation reactant mixture, in order to remedy the volatilization of lithium in the high-temperature calcination process, must increase the consumption of lithium compound in right amount, but because this reaction can not be in roasting under the excessive temperature, can not roasting long-time excessively, the excessive existence that can cause dephasign in the product too much of lithium compound.Therefore in reactant ratio, should guarantee that Li/ (Ni+Co+M) is between 1.01～1.10.
Li
aNi
1-b-cCo
bM
cO
2Material has different structures under high temperature and low temperature, and has only the high temperature phase structure of six side's stratiform rock salt structure to have electro-chemical activity, therefore need be with the product quenching to keep the high temperature phase structure of product.
The present invention is further illustrated below in conjunction with example.
First: about the example of reaction condition
With particle diameter is the high cobalt hydroxide nickel that is shaped as sphere or elliposoidal of 8～10 μ m
0.81Co
0.19(OH)
2After mixing with the lithium carbonate ball milling of 0.52 times of molar equivalent, roasting under the various conditions shown in the table 1 obtains the product of different structure respectively.The product of different structure is done following test and example of making battery respectively and is compared battery:
Utilize powder x-ray diffraction (Cu-K α) that product is carried out structure determination, whether check exists the lithium carbonate dephasign.
After the product that obtains is crossed 400 orders (bore 38.5 μ m) screen cloth, carrying out SEM (with the JSM-5610 test of JEOL company) observes, amplify 2000 times and 10000 times respectively, observe the size and the form of the small crystals particle (primary particle) of second particle and formation second particle.
Utilize particle size distribution measuring instrument (U.S. Honeywell Microtarc X100 tester) to measure the particle size distribution of product, the D of record product
50With D
10Value.
Get product 100g, place the even scale cylinder of elongated shape, this cylinder is highly freely dropped on the rubber slab from 50cm, repeat to read after 100 times the sample volume in the cylinder, calculate ram-jolt density.
Polyvinylidene fluoride (PVDF) is dissolved in the N-methyl pyrrolidone (NMP) at 120 ℃, after respectively the PVDF of the lithium nickel cobalt composite oxide of metal positive electrode of drying, acetylene black (conductive agent) and dissolving fully being mixed with weight ratio at 85: 10: 5, more than the dry 4h, obtain the positive electrode mixture.
With the button cell is example, carries out further specifying of battery performance:
Taking by weighing positive electrode mixture 0.102g, is collector with salt acid treatment and dried thin empty nickel screen, is pressed into the disk of φ 13mm diameter under 10Mpa pressure.Disk is placed 4h under 160 ℃ in vacuum drying oven, to disperse binding agent.So just obtained the needed positive plate of preparation battery.
In the glove box of Ar atmosphere, as shown in Figure 4, with positive plate 4, as negative pole removed the Li sheet 2 of the φ 16mm diameter of oxide on surface, polyethylene porous membrane 3, anode cover 6, negative electrode casing 1 and insulating washer 5 as barrier film is assembled into button cell.Use the lithium hexafluoro phosphate (LiPF of 1mol/L in the battery
6) as electrolyte, ethylene fat (EC) that use equal-volume ratio mixes and dimethyl carbonate (DMC) are as electrolyte.
Button cell after the preparation can detect after placing 1h.With the 1mA electric current battery is charged, reach 4.2V until open circuit voltage, placing behind the 30min with 1mA current discharge to battery open circuit voltage is 3.0V, the gained discharge capacity is discharge capacity first, can obtain first discharge specific capacity with (discharge capacity first)/(positive electrode consumption), unit is mAh/g.
Repeatedly battery is discharged and recharged with the above-mentioned condition that discharges and recharges, repeat 100 times after, can obtain 100 circulation back capability retentions according to (100 circulation back capability retention)=(the 100th discharge capacity)/(discharge capacity first) * 100%.
Get and newly prepare the button cell that discharges and recharges, with the 1mA electric current battery is charged, reach 4.2V until open circuit voltage, placing behind the 30min with 1mA current discharge to battery open circuit voltage is 3.0V, and the gained discharge capacity is recorded as (1mA discharge capacity); With the 1mA electric current battery is charged, reach 4.2V until open circuit voltage, placing behind the 30min with 5mA current discharge to battery open circuit voltage is 3.0V, and the gained discharge capacity is recorded as (5mA discharge capacity).Can obtain the multiplying power current discharge properties according to (multiplying power current discharge properties)=(5mA discharge capacity)/(1mA discharge capacity).
By above-mentioned condition and test experiments, according to the listed roasting condition of table 1, do embodiment 1～6 and comparative example 1～5, every test result sees Table 1.
Table 1
(continuing) table 1
| The experiment number | First section temperature (℃)/time (h) | Second section temperature (℃)/time (h) | Calcination atmosphere | Whether there is the lithium carbonate dephasign | Offspring form/size (μ m) | Primary particle form/size (μ m) | Particle size distribution D 50/D 10 (μm) | Ram-jolt density (g/cm 3) |
| Embodiment 1 | 600/8 | 750/20 | Oxygen | Do not have | Ball/11.5 | Ball/2.0 | 11.8/6.8 | 2.45 |
| Embodiment 2 | 650/6 | 750/20 | Oxygen | Do not have | Ball/11.5 | Ball/2.0 | 11.7/6.6 | 2.43 |
| Embodiment 3 | 700/1 | 800/16 | Oxygen | Do not have | Ball/12.0 | Ball/2.5 | 12.0/6.6 | 2.52 |
| Embodiment 4 | 650/6 | 800/16 | Oxygen | Do not have | Ball/12.0 | Ball/2.5 | 12.2/6.9 | 2.51 |
| Embodiment 5 | 650/6 | 850/12 | Oxygen | Do not have | Ball/13.0 | Ball/3.0 | 12.9/6.5 | 2.48 |
| Embodiment 6 | 650/6 | 900/8 | Oxygen | Do not have | Ball/14.0 | Ball/3.5 | 14.4/6.8 | 2.44 |
| Comparative Examples 1 | 500/10 | 800/16 | Oxygen | Do not have | Irregular/13.0 | Irregular/3.0 | 13.3/7.0 | 2.10 |
| Comparative Examples 2 | 750/1 | 800/16 | Oxygen | Do not have | Irregular/11.0 | Irregular/2.0 | 11.6/6.2 | 2.18 |
| Comparative Examples 3 | 650/6 | 700/30 | Oxygen | Have | Ball/10.0 | Ball/0.2 | 9.8/4.4 | 2.48 |
| Comparative Examples 4 | 650/6 | 1000/4 | Oxygen | Do not have | Do not have | Ball/5.5 | 5.2/2.8 | 1.89 |
| Comparative Examples 5 | 650/6 | 800/16 | Air | Have | Burr ball/10.0 | Irregular/0.5 | 10.4/5.5 | 2.03 |
| The experiment number | First section temperature (℃)/time (h) | Second section temperature (℃)/time (h) | Calcination atmosphere | First discharge specific capacity (mAh/g) | 100 circulation volume conservation rates (%) | Multiplying power current discharge properties (%) |
| Embodiment 1 | 600/8 | 750/20 | Oxygen | 178 | 92.7 | 78.4 |
| Embodiment 2 | 650/6 | 750/20 | Oxygen | 180 | 92.4 | 77.9 |
| Embodiment 3 | 700/1 | 800/16 | Oxygen | 181 | 92 0 | 78.7 |
| Embodiment 4 | 650/6 | 800/16 | Oxygen | 185 | 92.8 | 78.6 |
| Embodiment 5 | 650/6 | 850/12 | Oxygen | 183 | 91.9 | 78.2 |
| Embodiment 6 | 650/6 | 900/8 | Oxygen | 184 | 92.4 | 76.2 |
| Comparative Examples 1 | 500/10 | 800/16 | Oxygen | 176 | 85.4 | 50.3 |
| Comparative Examples 2 | 750/1 | 800/16 | Oxygen | 178 | 83.2 | 54.9 |
| Comparative Examples 3 | 650/6 | 700/30 | Oxygen | 156 | 71.9 | 56.7 |
| Comparative Examples 4 | 650/6 | 1000/4 | Oxygen | 182 | 86.4 | 45.1 |
| Comparative Examples 5 | 650/6 | 800/16 | Air | 160 | 77.0 | 60.4 |
Second portion: about the example of Co content
Press and select the different Ni of b value in the table 2
1-bCo
b(OH)
2Be raw material, do embodiment 7～12 and comparative example 6～9, other conditions are identical with embodiment in the first 4.Product is substantially the same manner as Example 4 at aspects such as form, particle diameter, ram-jolt density, and other test results see Table 2:
Table 2
| The experiment number | Ni 1-yCo y(OH) 2Middle b value | First discharge specific capacity (mAh/g) | 100 circulation volume conservation rates (%) | Multiplying power current discharge properties (%) |
| Embodiment 7 | 0.01 | 192 | 85.5 | 64.5 |
| Embodiment 8 | 0.05 | 190 | 87.8 | 73.3 |
| Embodiment 9 | 0.10 | 187 | 91.2 | 77.4 |
| Embodiment 10 | 0.19 | 185 | 92.8 | 78.6 |
| Embodiment 11 | 0.25 | 180 | 92.7 | 78.6 |
| Embodiment 12 | 0.30 | 175 | 93.1 | 78.9 |
| Comparative Examples 6 | 0 | 205 | 82.2 | 47.1 |
| Comparative Examples 7 | 0.35 | 170 | 93.5 | 79.2 |
| Comparative Examples 8 | 0.5 | 153 | 94.1 | 80.8 |
| Comparative Examples 9 | 1 | 145 | 95.4 | 82.0 |
Third part: about Li
aNi
1-b-cCo
bM
cO
2The example of subgrain and small crystals particle volume ratio.
Prepare lithium nickel peroxide positive electrode by the embodiment of first 4 methods.
Get the positive electrode that partly obtains and sieve, collect the above second particle of 8 μ m, be labeled as A.
Get the positive electrode that part obtains again, grind, all become the small crystals particle, be labeled as B by grinding until second particle with grinder.
Press mixed A and B in the table 3, be embodiment 13～15 and comparative example 10～12 carries out particle size distribution and ram-jolt density measurement, and make battery and test, the results are shown in Table 3 by first's method:
Table 3
| The experiment number | A: B (volume ratio) | D 10/μm | Ram-jolt density (g/cm 3) | First discharge specific capacity (mAh/g) | 100 circulation volume conservation rates (%) | Multiplying power current discharge properties (%) |
| Embodiment 13 | 100∶0 | 8.2 | 2.57 | 185 | 92.6 | 78.2 |
| Embodiment 14 | 95∶5 | 8.0 | 2.54 | 186 | 92.9 | 78.8 |
| Embodiment 15 | 90∶10 | 6.4 | 2.52 | 185 | 92.8 | 78.6 |
| Comparative Examples 10 | 85∶15 | 34 | 2.29 | 172 | 93.0 | 74.3 |
| Comparative Examples 11 | 50∶50 | 1.2 | 1.85 | 165 | 93.5 | 56.1 |
| Comparative Examples 12 | 0∶100 | 0.5 | 1.60 | 157 | 93.6 | 53.7 |
As seen from the above table, when this positive electrode active materials is carried out particle size distribution test, D
10Be more than the 6 μ m, the small crystals particle volume that does not promptly form second particle in this system is no more than 10% of cumulative volume, battery performance good electrical properties.
Third part: about product Li
aNi
1-b-cCo
bM
cO
2The example of form.
Comparative Examples 13:
Synthetic method is identical with embodiment 4, and difference is the high cobalt hydroxide nickel that adopts
0.81Co
0.19(OH)
2Be the irregularly shaped of 8～10 μ m.
The synthetic lithium nickel cobalt metal oxide cathode active material that obtains is carried out sem analysis and ram-jolt density measurement, and make button cell, detect its first discharge specific capacity and multiplying power current discharge properties (table 4) by the method for first.
Table 4
| The experiment number | The secondary spherical shape | Ram-jolt density (g/cm 3) | First discharge specific capacity (mAh/g) | Multiplying power current discharge properties (%) |
| | Spherical | 2.51 | 185 | 78.6 |
| Comparative Examples 13 | Sheet, tetrahedral etc. are irregularly shaped | 2.09 | 178 | 60.4 |
From top embodiment and comparative example as can be seen, the lithium-nickel-cobalt-oxygen thing positive electrode synthetic by the inventive method has the second particle structure that is combined into by the small crystals particle, and second particle is sphere or elliposoidal, improved the ram-jolt density of positive electrode.Simultaneously, use the secondary cell of this positive electrode to have higher discharge capacity, charge-discharge performance and multiplying power current discharge properties preferably.
Claims (5)
1, a kind of non-aqueous secondary batteries positive electrode active materials is characterized in that:
(1) with the chemical formulation is LiaNi
1-b-cCo
bM
cO
2, 0.97≤a≤1.05,0.01≤b≤0.30,0≤c≤0.10 wherein, M is one or more among Mn, Al, Ti, Cr, Mg, Ca, V, Fe and the Zr;
(2) this positive electrode active materials is made of the second particle that small crystals particle and small crystals particle aggregation form, and wherein the small crystals grain diameter is 0.5～4 μ m, and the second particle particle diameter is 10～40 μ m, and small crystals particle volume≤cumulative volume 10%.
2, non-aqueous secondary batteries positive electrode active materials as claimed in claim 1 is characterized in that: described second particle is to be mutually combined by the small crystals particle in sintering process and constantly increase the Li that grows up and form
aNi
1-b-cCo
bM
cO
2Crystal grain is shaped as sphere or elliposoidal.
3, a kind of arbitrary non-aqueous secondary batteries as claimed in claim 1 or 2 is characterized in that with the preparation method of positive electrode active materials the method comprises the steps:
(1) preparation of high cobalt nickel hydroxide: employing adds ammoniacal liquor and prepares high cobalt nickel hydroxide in cobaltous sulfate that mixes and nickel sulfate solution, its structural table is shown Ni
1-bCo
b(OH)
2, 0.01≤b≤0.30 wherein;
(2) lithium nickel cobalt composite oxide of metal Li
aNi
1-b-cCo
bM
cO
2Preparation:
A. first section roasting: get lithium compound and above-mentioned Ni
1-bCo
b(OH)
2, the M compound mixed in the ratio ball milling of Li/ (Ni+Co+M) between 1.01～1.10, the roasting temperature under the oxygen atmosphere, between 600 ℃ to 720 ℃ 1～10 hour;
B. second section roasting: with the product of step a again the roasting temperature under the oxygen atmosphere, between 750 ℃ to 900 ℃ 8～20 hours;
C. step b products therefrom quenching, ball milling, screening can be obtained described non-aqueous secondary batteries positive electrode active materials.
4, non-aqueous secondary batteries as claimed in claim 3 is characterized in that: the high cobalt hydroxide nickel of control in the step (1) with the preparation method of positive electrode active materials
1-bCo
b(OH)
2Be shaped as sphere or elliposoidal, average grain diameter D
50〉=8 μ m, D
10〉=4 μ m, D
90≤ 30 μ m.
5, a kind of non-aqueous secondary batteries comprises following element:
(1) negative pole comprises among the material that can embed and separate out lithium ion, lithium metal, the lithium alloy one or more;
(2) positive pole comprises as any positive electrode active materials in claim 1 or 2;
(3) electrolyte contacts with anodal with described negative pole.
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| US10/823,931 US20040191161A1 (en) | 2002-11-19 | 2004-04-14 | Compounds of lithium nickel cobalt metal oxide and the methods of their fabrication |
| US10/841,760 US20040223906A1 (en) | 2003-05-09 | 2004-05-08 | Lithium nickel cobalt oxides and their methods of fabrication |
| US10/918,580 US7771875B2 (en) | 2003-08-15 | 2004-08-13 | Positive electrodes for rechargeable batteries |
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| JP4781004B2 (en) | 2005-04-28 | 2011-09-28 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery |
| CN113571772A (en) * | 2005-10-20 | 2021-10-29 | 三菱化学株式会社 | Lithium secondary battery and nonaqueous electrolyte used therein |
| EP3217463B1 (en) | 2005-10-20 | 2019-06-05 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| JP2009259798A (en) | 2008-03-19 | 2009-11-05 | Panasonic Corp | Non-aqueous electrolyte secondary battery |
| JP4807467B1 (en) * | 2010-07-23 | 2011-11-02 | 住友金属鉱山株式会社 | Cathode active material for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| CN103985856A (en) * | 2014-05-16 | 2014-08-13 | 海宁美达瑞新材料科技有限公司 | Nickel cobalt lithium aluminate positive material and preparation method thereof |
| WO2017150055A1 (en) * | 2016-03-04 | 2017-09-08 | パナソニックＩｐマネジメント株式会社 | Nonaqueous-electrolyte secondary battery |
| EP3642160B1 (en) * | 2017-06-23 | 2021-01-20 | Umicore | Beta-nickel hydroxide doped with aluminum |
| KR102306545B1 (en) | 2017-10-19 | 2021-09-30 | 주식회사 엘지에너지솔루션 | Positive electrode material for lithium secondary battery, preparing method of the same, positive electrode and lithium secondary battery including the same |
| CN114430037B (en) * | 2022-04-06 | 2022-07-15 | 比亚迪股份有限公司 | A kind of positive electrode material and its application |
| CN115224346B (en) * | 2022-07-20 | 2024-06-18 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
| CN116111081A (en) * | 2022-10-31 | 2023-05-12 | 北京当升材料科技股份有限公司 | Agglomeration type multielement cathode material, preparation method and application thereof, and lithium ion battery |
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