CN1284756A - Active positive-pole material for lithium ion secondary cell and its preparation and use - Google Patents
Active positive-pole material for lithium ion secondary cell and its preparation and use Download PDFInfo
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- CN1284756A CN1284756A CN99113982A CN99113982A CN1284756A CN 1284756 A CN1284756 A CN 1284756A CN 99113982 A CN99113982 A CN 99113982A CN 99113982 A CN99113982 A CN 99113982A CN 1284756 A CN1284756 A CN 1284756A
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- lithium
- containing compound
- positive electrode
- electrode active
- sintering
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 title claims description 37
- 238000002360 preparation method Methods 0.000 title description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract 4
- 239000002245 particle Substances 0.000 claims description 22
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 17
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 14
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910018040 Li 1+x Ni Inorganic materials 0.000 claims 2
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000006182 cathode active material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000001413 cellular effect Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 8
- 150000001869 cobalt compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- -1 oxonium ion Chemical class 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910006784 Li1+xNi Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910015947 LixNi Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 102100025490 Slit homolog 1 protein Human genes 0.000 description 1
- 101710123186 Slit homolog 1 protein Proteins 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- LGDAGYXJBDILKZ-UHFFFAOYSA-N [2-methyl-1,1-dioxo-3-(pyridin-2-ylcarbamoyl)-1$l^{6},2-benzothiazin-4-yl] 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 LGDAGYXJBDILKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
公开了一种用于锂离子二次电池通式为Lil+xNiyCol－yO2+z的正极活性材料;其中0<x<0.2,0.6≤y≤0.9,0≤z≤0.2,它是用下列方法制得的:(a)将一定比例的含锂化合物、含钴化合物和含镍化合物混合并研磨;(b)将得到的混合物模压成蜂窝状的块料;(c)将所述块料在含氧气氛中烧结。由于试样压成蜂窝状后再烧结,与压成实芯状的试样相比,由于试样内芯部分能与氧气充分接触,从而极大地提高了产品的电化学性能。还公开了该正极活性材料的制造方法。Disclosed is a positive electrode active material for lithium ion secondary batteries whose general formula is Li l+x Ni y Co l－y O 2+z ; wherein 0<x<0.2, 0.6≤y≤0.9, 0≤z≤ 0.2, which is prepared by the following method: (a) mixing and grinding certain proportions of lithium-containing compound, cobalt-containing compound and nickel-containing compound; (b) molding the obtained mixture into a honeycomb block; (c ) sintering the blocks in an oxygen-containing atmosphere. Because the sample is pressed into a honeycomb shape and then sintered, compared with the sample pressed into a solid core shape, the electrochemical performance of the product is greatly improved because the inner core part of the sample can fully contact with oxygen. Also disclosed is a method for manufacturing the cathode active material.
Description
The present invention relates to be used for positive electrode active materials and the manufacture method and the purposes of lithium rechargeable battery, specifically, the present invention relates to be used for the Li of lithium rechargeable battery
1+yNi
yCo
1-yO
2+zPositive electrode active materials (wherein 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2) and manufacture method and purposes.
Lithium rechargeable battery have the life-span long, specific capacity is high, do not have advantages such as " memories ", thereby be widely used in various small portable apparatus, as mobile phone, portable computer etc.
At present, the positive electrode active materials of widely used lithium rechargeable battery has LiCoO
2LiCoO
2Near discharge platform (to lithium) 3.8-4V, theoretical specific capacity is 274mAh/g.During use, in order to prevent electrolytical decomposition, charging voltage is limited near the 4.3V (to lithium):
Therefore its actual specific capacity is about about 140mAh/g.Because Co
3+In air when heating more stable, therefore think LiCoO
2Be than the material that is easier to synthesize.The specific descriptions of this positive electrode active materials can be referring to United States Patent (USP) 3,945, and 848 and 4,340,652.But because the price of cobalt is more expensive, the cost of the feasible positive electrode active materials that makes thus is higher.
LiNiO
2It is the positive electrode active materials of the superior another kind of lithium rechargeable battery of chemical property.Its specific capacity is up to 274mAh/g.The embedding voltage range of taking off of lithium is 3.4-4.2V, and its price only is 1/3 of a cobalt.But, because Ni
3+At high temperature unstable, synthetic LiNiO
2The time, Ni is often arranged
2+Supervene.These Ni
2+Remove and to capture in the lattice Ni of 3b position on the nickel dam
3+Outside the position, also invade and occupy the locational Li of 3a in the lattice in the lithium layer
+The position forms the ion mixed layer, and its molecular formula can be expressed as:
[Li
+ 1-dNi
2+ d]
3a[Ni
3+ 1-dNi
2+ d]
3b[O
2- 2]
6c
Its consequence is the locational Li of 3a
+Content reduce, also increased the active Ni of non-electrochemical simultaneously
2+Content, make reversible capacity reduce.Because Ni
2+Ionic radius (r
0=0.068nm) greater than Ni
3+Ionic radius (r
0=0.056nm), so Ni
2+Existence make the nickel dam spacing increase, stability of structure is affected, the cycle performance of material degenerates.
LiNiO
2And LiCoO
2Have and α-NaFeO
2Identical cube rock salt crystal structure.Be closs packing with the oxonium ion in the lattice, Li
+, Co
3+Or Ni
3+Be on the closely packed octahedral position of oxonium ion.At LiNiO
2In mix the Co atom, form Li
1+xNi
yCo
1-yO
2+z, in the whole interval of y=0 to y=1, can form good solid solution and keep crystallographic system constant.Co
3+Ratio of ionic radii Ni
2+And Ni
3+All little, Co when high temperature is synthetic in oxygen-containing atmosphere
3+Good stability, Li
1+xNi
yCo
1-yO
2+zIn Co
3+Account for the 3b position, can effectively suppress Ni
2+The antiposition ion, reduced the thickness of nickel ion layer simultaneously, play rock-steady structure thereby improve cycle characteristics.
Tsutomu Ohzuku etc. are at Electrochimica Acta vol.38, and No.9 discloses a kind of Li of using in 1993
2CO
2, CoCO
3And NiCO
3Compressing tablet prepares LiNi
yCo
1-yO
2The method of composite oxides.But the lithium battery that the composite oxides that make with this method constitute its capacity when y＜1 is not more than 150mAh/g.
Therefore, need a kind of positive electrode active materials that is used for lithium rechargeable battery of exploitation with higher chemical property and moderate cost.
The purpose of this invention is to provide a kind of have higher chemical property and the moderate positive electrode active materials that is used for lithium rechargeable battery;
Another object of the present invention provides a kind of manufacture method that is used for the positive electrode active materials of lithium rechargeable battery.The lithium rechargeable battery that the positive electrode active materials that makes in this way constitutes has good charge-discharge characteristic.
Further object of the present invention provides a kind of lithium rechargeable battery that makes with positive electrode active materials of the present invention.
The invention provides a kind of general formula that is used for lithium rechargeable battery is Li
1+xNi
yCo
1-yO
2+zPositive electrode active materials, 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2 wherein is characterized in that it makes with following method:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into cellular block of material;
(c) with described block of material sintering in oxygen-containing atmosphere.
It is Li that the present invention also provides a kind of lithium rechargeable battery general formula that is used for
1+xNi
yCo
1-yO
2+zThe manufacture method of positive electrode active materials, 0＜x in the described general formula＜0.2,0.6≤y≤0.9,0≤z≤0.2, this method comprises:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into the piece material;
(c) with described block of material sintering in oxygen-containing atmosphere; And optional
(d) the agglomerate abrasive lapping that makes is pulverized, be molded into the step of cellular block of material and sintering again;
It is characterized in that the piece material that is molded into is cellular in step (b).
Below the present invention will be described in more detail.
Fig. 1 is the used oxygen ultraviolet light active device of better example of the present invention;
Fig. 2 a is the typical x-ray diffraction pattern of comparative example 1 and comparative example 2 samples;
Fig. 2 b is the typical x-ray diffraction pattern of embodiment 14 samples;
Fig. 3 a is charge-discharge current potential-time (V (﹠amp of embodiment 4 products; Li)-t) graph of a relation;
Fig. 3 b is the specific capacity-cycle-index graph of a relation of embodiment 4 products;
Fig. 4 a is charge-discharge current potential-time (V (﹠amp of embodiment 2 products; Li)-t) graph of a relation;
Fig. 4 b is the specific capacity-cycle-index graph of a relation of embodiment 2 products.
The general formula that the present invention is used for the positive electrode active materials of lithium rechargeable battery is Li1+xNi
yCo
1-yO
2+z, 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2 wherein, it makes with following method:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into cellular block of material;
(c) with described block of material sintering in oxygen-containing atmosphere.
Lithium-containing compound for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various lithium-containing compounds of battery, its example includes, but are not limited to lithium carbonate, lithium nitrate and lithia. Wherein Better be lithium carbonate and lithium nitrate, but because lithium nitrate at high temperature can be emitted nitrogen dioxide gas, pollute ring Therefore border, lithium carbonate preferably.
Cobalt compound for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various cobalt compounds of battery, its example includes, but are not limited to cobalt sesquioxide, cobaltosic oxide and nitric acid Cobalt etc. Better be cobalt sesquioxide and cobaltosic oxide, preferably cobalt sesquioxide.
Nickel compound containing for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various nickel compound containings of battery, its example includes, but are not limited to nickel sesquioxide and nickel nitrate etc. Better be Nickel sesquioxide.
When making positive electrode active materials of the present invention, earlier with a certain proportion of lithium-containing compound, cobalt compound and The powder ground and mixed of nickel compound containing, the particle diameter of described powder is without particular limitation, as long as this particle diameter is to reaching The object of the invention has no adverse effect and gets final product. But the particle diameter of these compounds is preferably the 1-20 micron.
According to required positive electrode active materials LixNi
yCo
1-yO
2+z, those of ordinary skill in the art can be easily Know the ratio between the consumption of lithium-containing compound, cobalt compound and nickel compound containing. And this area is general Logical technical staff is appreciated that by control sintering temperature and reaction atmosphere, can obtains required z value.
Subsequently, the stamping of powder through mixing is become cellular block of material. At an example preferably of the present invention In, the piece material that makes is the piece material of similar structure of honeycomb briquette. Then, with cellular block of material making oxygenous Carry out sintering in the atmosphere. The agglomerating plant that the present invention uses is equipment as known in the art, such as the SG2-3-12 type Muffle furnace (available from Shanghai Industrial pottery mechanical ﹠ electrical corporation), employed oxygen-containing atmosphere can be air, purity oxygen Or active improved oxygen. In order to increase contacting of reactant and oxygen, prevent the divalent metal nickel ion, institute Stating oxygen-containing atmosphere better is purity oxygen or active improved oxygen, preferably active improved oxygen.
Fig. 1 is the used oxygen ultraviolet light active device schematic diagram of better example of the present invention, described device bag Draw together oxygen air inlet 1, quartz socket tube 2 and oxygen gas outlet 3. The inner tube of quartz socket tube 2 is equipped with the strip purple Outer light pipe. Oxygen enters quartz socket tube 2 from oxygen air inlet 1 during use, is subjected to there the ultraviolet light pipe and sends The irradiation of ultraviolet light, form the mist of excitation state, ozone and the oxygen of various oxygen, described mist Enter sintering furnace through oxygen gas outlet 3.
The ultraviolet light pipe that fills in the inner tube of quartz socket tube 2 is without particular limitation. In an example of the present invention In, this ultraviolet light pipe is low pressure mercury lamp, the wave-length coverage of the ultraviolet light that it sends is 200-400nm.
The sintering temperature of preparation positive electrode active materials of the present invention is 500-900 ℃. If temperature is lower than 500 ℃, Then do not reach the purpose of sintering; If temperature is higher than 900 ℃, then the chemical property of product can descend. Better Sintering temperature be 650-900 ℃, be preferably 750-800 ℃. When heat-agglomerating, can earlier temperature be risen to 500-600 ℃, better rise to 550-600 ℃ and keep a period of time to remove the moisture in the raw material, simultaneously so that The fusing of lithium carbonate and decomposable process slowly carry out, and produce new inhomogeneous with the raw material that prevents from originally mixing The zone is warming up to subsequently sintering temperature again and keeps the regular hour in order to make the material tight burning in this temperature. But this substep temperature-rise period is optional. The time of sintering is different with the temperature of sintering. In general burn More high then required time of the temperature of knot is more short. Those of ordinary skill in the art can be easily according to the temperature of sintering Degree is determined the time of sintering. At 500-600 ℃, more fortunately under 550-600 ℃ the preheat temperature, preheating time Be generally 4-8 hour, be preferably 5-6 hour. Sintering time under described sintering temperature is generally 10-17 Hour, be preferably 13-15 hour.
In order to guarantee the homogeneity of product, when making positive electrode active materials of the present invention, can be cellular with what make The piece material is pulverized, and grinds, and is molded into cellular block of material and sintering again. These steps can repeatedly, repeat usually Two to three times, make the product that makes have the performance of homogeneous. Can cellular block of abrasive lapping powder will be obtained finally Broken, and make the positive pole of required lithium ion battery with conductive material and binding agent.
Positive electrode active materials L of the present invention
1+xNi
yCo
1-yO
2+zAdopt the powder solid phase reaction method to make.During fabrication raw material is fully mixed and grind after be molded into similar cellular structure, increased the contact area of reactant and oxygen, suppressed the formation of bivalent nickel ion, thereby obtained the good single-phase product of crystal structure.The lithium rechargeable battery that makes with positive electrode active materials of the present invention has high specific capacity and good charge-discharge performance.
To further specify the present invention by embodiment below.
Embodiment
In the following embodiments, use the performance of the positive electrode active materials that following measurement of test method makes.
The specific capacity method of testing
The sample that 85 weight % the following example are made adds in NMP (N-N-methyl-2-2-pyrrolidone N-(the N-methy1-2-pyrrolidinone)) solution with 10 weight % acetylene blacks and 5 weight %PVDF (polyvinylidene fluoride (polyvinylidene fluoride)), it is fully stirred into pasty state and be coated on the aluminium foil, form the thick film of about 0.1mm.Place vacuum drying oven 130 ℃ of bakings 12 hours, as positive pole on membrane aluminium foil; With the lithium sheet is negative pole; With EC (vinyl carbonate (ethylene carbonate)): DMC (dimethyl carbonate (dimethyl carbonate))=50: 50 (weight ratio), 1M LiPF6 (lithium hexafluorophosphate) is an electrolyte, constitutes lithium battery.
Charging and discharging currents size during test becomes according to the size of electroactive substance, is controlled near the 14mA/g.The about 0.2-0.4mA/cm of current density
2, voltage range is 4.3-2.5V, the ambient temperature of battery is 30 ℃.
The atomic composition ratio of metallic element
Adopt the Solaar 939 type Atomic Absorption Spectrometers of Britain UNICAM that Li, Ni and Co content are measured.The content of oxygen adopts deduction method to calculate and gets, and promptly is calculated as follows:
W
o=W
Always-W
Li-W
Ni-W
Co
Wherein, W
Always-sampling total weight when analyzing;
W
LiThe content of-lithium;
W
NiThe content of-nickel;
W
CoThe content of-cobalt;
More than 4 parameters be actual measurement weight, W
oFor the weight of oxygen, by W
o/ M
o(M
0Atomic weight for oxygen) can try to achieve the atom numerical value of oxygen in the product molecular formula.
Structural analysis
Adopt the DMAX-γ β type powder X-ray-optical diffraction instrument of Japanese motor of science to measure.Copper target k α 1/40kV/100mA, scatter slit 1 degree receives slit 0.3mm, sweep speed 4 degree/minute.
Preparation Li
1.02Ni
0.9Co
0.1O
2.05Positive electrode active materials
With 1.1 moles of particle diameters be 1 micron lithium nitrate, 0.45 mole of particle diameter be 10 microns nickel sesquioxide and 0.033 mole of particle diameter be 2 microns cobaltosic oxide (all available from Shanghai reagent two factories, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with powder compressing machine (the 75yp-15z type is available from Tianjin Keqi High Technology Corp.).The piece material that obtains is placed sintering furnace (SG2-3-12 type, available from Shanghai industrial ceramics mechanical ﹠ electrical corporation) in oxygen atmosphere, heat with the heating rate about 3 ℃/min, with this piece material at 600 ℃ of constant temperature after 4 hours, be warming up to 780 ℃ and keeping under this temperature about 15 hours again, stop heating subsequently, make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 15 hours subsequently naturally in 780 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature about 15 hours in 780 ℃ sintering furnace stops heating after being cooled to 300 ℃ with 1 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.02 as a result, and the content of nickel is 0.90, and the content of cobalt is 0.1, calculates to such an extent that the content of oxygen is 2.05.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 169mAh/g, and specific discharge capacity is 147mAh/g.X-ray diffraction pattern is shown in Fig. 2 b.By this figure as seen, (102) peak of the product that makes and (006) peak obviously separate, and (018) peak and (110) peak also obviously separate.
Preparation Li
1.03Ni
0.6Co
0.4O
2.03Positive electrode active materials
With 0.55 mole of particle diameter be 10 microns lithium carbonate, 0.3 mole of particle diameter be 1 micron nickel sesquioxide and 0.134 mole of particle diameter be 20 microns cobaltosic oxide (all available from Shanghai chemical reagent work, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with 76yp-15z type powder compressing machine.Place SG2-3-12 type sintering furnace at ultraviolet light (low pressure mercury lamp in the piece material that obtains, heat with the heating rate about 5 ℃/min in the oxygen atmosphere that λ=200-400nm) activates, with this piece material at 600 ℃ of constant temperature after 6 hours, be warming up to 800 ℃ and keeping under this temperature about 13 hours again, stop heating subsequently and make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 13 hours subsequently naturally in 800 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature is about 13 hours in 800 ℃ sintering furnace, stops heating after being cooled to 300 ℃ with about 1.5 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.03 as a result, and the content of nickel is 0.59, and the content of cobalt is 0.41, calculates to such an extent that the content of oxygen is 2.03.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 165mAh/g, and specific discharge capacity is 138mAh/g.Its charge-discharge current potential-time (V (﹠amp; Li)-t) graph of a relation is shown in Fig. 4 a, and specific capacity-cycle-index graph of a relation is shown in Fig. 4 b.X-ray diffraction pattern is similar to Fig. 2 b.
Preparation Li
1.01Ni
0.75Co
0.25O
2.01Positive electrode active materials
Press the identical method of embodiment 1, but being to use 1.1 moles of particle diameters is that 20 microns lithium nitrate, 0.375 mole of particle diameter are that the cobalt sesquioxide that 20 microns nickel sesquioxide and 0.125 mole of particle diameter are 1 micron prepares sample, the preheat temperature of using is 550 ℃, the time that keeps under this temperature is 8 hours, sintering temperature is 900 ℃, and sintering time is about 10 hours.The content of lithium is 1.01 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.75, and the content of cobalt is 0.25, and the content of the oxygen that calculates is 2.01.
The charge and discharge cycles result of the test: charging and discharging capacity is 180mAh/g for the first time, and specific discharge capacity is 143mAh/g.X-ray diffraction pattern is similar to Fig. 2 b.
Embodiment 4
Preparation Li
1.04Ni
0.9Co
0.1O
2.05Positive electrode active materials
Pressing the identical method of embodiment 1, is that 1 micron lithium carbonate, 0.45 mole of particle diameter are that the cobalt sesquioxide that 7 microns nickel sesquioxide and 0.05 mole of particle diameter are 5 microns prepares sample but be to use 0.55 mole of particle diameter.The content of lithium is 1.04 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.90, and the content of cobalt is 0.11, and the content of the oxygen that calculates is 2.05.
The charge and discharge cycles result of the test: charging and discharging capacity is 205mAh/g for the first time, and specific discharge capacity is 175mAh/g.It discharges and recharges current potential-time (V (﹠amp; Li)-t) relation is shown in Fig. 3 a, and specific capacity-cycle-index concerns that x-ray diffraction pattern is similar to Fig. 2 b shown in Fig. 3 b.
Preparation Li
1.05Ni
0.65Co
0.35O
2.19
With 0.55 mole of particle diameter be 8 microns lithia, 0.22 mole of particle diameter be 20 microns nickel nitrate and 0.12 mole of particle diameter be 20 microns cobalt nitrate (all available from Shanghai chemical reagent work, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with 76yp-15z type powder compressing machine.The piece material that obtains is placed the heating rate heating of SG2-3-12 type sintering furnace about oxygen atmosphere is with 2 ℃/min, this piece material at 600 ℃ of constant temperature after 5 hours, is warming up to 650 ℃ and keeping about 24 hours under this temperature again.Stop heating subsequently, make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 24 hours subsequently naturally in 650 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature is about 24 hours in 650 ℃ sintering furnace, stops heating after being cooled to 300 ℃ with about 1.5 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.05 as a result, and the content of nickel is 0.66, and the content of cobalt is 0.35, calculates to such an extent that the content of oxygen is 2.19.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 176mAh/g, and specific discharge capacity is 130mAh/g.Its charge-discharge current potential-time (V (﹠amp; Li)-t) graph of a relation is shown in Fig. 4 a, and specific capacity-cycle-index graph of a relation is shown in Fig. 4 b.X-ray diffraction pattern is similar to Fig. 2 b.
Embodiment 6
Preparation Li
1.19Ni
0.7Co
0.3O
2.09
Press the identical method of embodiment 5, but being to use 0.62 mole of particle diameter is that 1 micron lithium carbonate, 0.35 mole of particle diameter are that the cobalt sesquioxide that 1 micron nickel sesquioxide and 0.15 mole of particle diameter are 1 micron prepares sample, preheat temperature is 550 ℃, and sintering temperature is 750 ℃.The content of lithium is 1.19 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.70, and the content of cobalt is 0.31, and the content of the oxygen that calculates is 2.09.
The charge and discharge cycles result of the test: charging and discharging capacity is 195 mAh/g for the first time, and specific discharge capacity is 170mAh/g.It discharges and recharges current potential-time (V (﹠amp; Li)-t) relation is shown in Fig. 3 a, and specific capacity-cycle-index concerns that x-ray diffraction pattern is similar to Fig. 2 b shown in Fig. 3 b.
Comparative example 1
Prepare sample by embodiment 4 identical methods, kept 10 hours but after grinding for the third time, cellular sample placed under 950 ℃ the temperature.The content of lithium is 0.97 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.90, and the content of cobalt is 0.11, and the content that calculates oxygen is 1.92.
The charge and discharge cycles result of the test: the charge ratio capacity is 163mAh/g for the first time, and specific discharge capacity is 121mAh/g.Shown in X-ray diffractogram and Fig. 2 a.
Comparative example 2
Prepare sample by embodiment 4 identical methods, but sample is compression molded into real pellet shape.The content of lithium is 1.08 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.91, and the content of cobalt is 0.11, and the content that calculates oxygen is 1.94.
The charge and discharge cycles result of the test: the charge ratio capacity is 177mAh/g for the first time, and specific discharge capacity is 129mAh/g.Shown in X-ray diffractogram and Fig. 2 a.
See by top embodiment, with sample be pressed into cellular after sintering again, compare with the sample that is pressed into real core shape because sample inner core part can fully contact with oxygen, thereby greatly improved the chemical property of product.
Although in conjunction with non-limiting instance the present invention is had been described in detail, those of ordinary skill in the art can easily carry out various changes and modifications to the present invention under the prerequisite that does not depart from spirit and scope of the invention.Scope of the present invention comprises this changes and improvements.
Claims (15)
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| CNB991139828A CN1156928C (en) | 1999-08-16 | 1999-08-16 | Positive electrode active material for lithium ion secondary battery, production method and use thereof |
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