CN101694877A - Lithium-ion secondary battery cathode active substance and process for preparation - Google Patents
Lithium-ion secondary battery cathode active substance and process for preparation Download PDFInfo
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- CN101694877A CN101694877A CN200910232893A CN200910232893A CN101694877A CN 101694877 A CN101694877 A CN 101694877A CN 200910232893 A CN200910232893 A CN 200910232893A CN 200910232893 A CN200910232893 A CN 200910232893A CN 101694877 A CN101694877 A CN 101694877A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract 4
- 239000013543 active substance Substances 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title abstract 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 119
- 239000010941 cobalt Substances 0.000 claims abstract description 119
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000010936 titanium Substances 0.000 claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 79
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000010955 niobium Substances 0.000 claims abstract description 78
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 78
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 75
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 74
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 65
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 44
- 238000000975 co-precipitation Methods 0.000 claims abstract description 34
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims description 81
- 239000002253 acid Substances 0.000 claims description 36
- 230000009466 transformation Effects 0.000 claims description 17
- 239000011149 active material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 229910013733 LiCo Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 2
- 229910012701 LiCo1-xMxO2 Inorganic materials 0.000 abstract 1
- 229910012938 LiCo1−xMxO2 Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 13
- 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 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
Abstract
The invention discloses a lithium-ion secondary battery cathode active substance and a process for preparation. The cathode active substance applied to a lithium-ion secondary battery is provided with lithium cobalt oxide of a hexagonal system, the lithium cobalt oxide is represented by the general formula (LiCo1-xMxO2 (M=Ti, Zr, V, Nb)) and obtained by mixing a cobalt compound serving as a cobalt source and a lithium compound serving as a lithium source according to a molar ratio of 1:1. Besides, titanium, zirconium, vanadium and niobium are added into the cobalt compound by means of coprecipitation, the addition quantity of the titanium is 0.01mol%-1mol% relative to the quantity of cobalt, and the addition quantities of the zirconium, the vanadium and the niobium are 0.01mol%-3mol% relative to the quantity of the cobalt. Further, the cobalt compound and the lithium compound are sintered for 18-20 hours in air at the temperature ranging from 880 DEG C to 920 DEG C through the procedures of coprecipitation, mixing and sintering. The lithium-ion secondary battery cathode active substance and the process for preparation have the advantages of not reducing battery capacity and charge-discharge efficiency and being capable of improving heat stability, rate performance and charge-discharge cycle performance.
Description
Technical field
The present invention relates to a kind of active material for anode of Li-ion secondary battery and manufacture method thereof.
Background technology
This year is along with the portability of machine, the development of wireless penetration, to small-sized, light weight and to have a requirement of nonaqueous electrolytic solution secondary batteries such as lithium rechargeable battery of high-energy-density more and more higher.As everyone knows, this nonaqueous electrolytic solution secondary battery has LiCoO with positive electrode active material
2, LiNiO
2, LiNi
0.8Co
0.2O
2, LiNi
0.33Co
0.33Mn
0.33O
2, LiMn
2O
4, LiFePO
4Composite oxides or phosphate Deng lithium and transition metal.
Wherein, use cobalt acid lithium (LiCoO
2) as positive electrode active material, use carbon such as lithium alloy, graphite, carbon fiber can obtain 4V level high voltage as the lithium rechargeable battery of negative pole, so be widely used as the battery with high-energy-density.
But, exist to use the lithium rechargeable battery of cobalt acid lithium, the cycle characteristics that causes because of the sub-stripping in cobalt source etc. and the problem of security feature variation.
Because cobalt acid lithium is in respect to the current potential more than the lithium 4V, therefore, when using it as the positive active material of rechargeable nonaqueous electrolytic battery, each repeated charge-discharge cycles has cobalt from anodal stripping.So, anodal variation, the problem that the capacity characteristic after the generation charge and discharge cycles, load characteristic reduce.For this reason, the Japan Patent spy opens and discloses following scheme in the 2004-047437 communique, has promptly added xenogenesis element M such as V, Cr, Fe, Mn, Ni, Al, Ti, Zr and obtained general formula LiCo when synthetic cobalt acid lithium
1-XM
XO
2The cobalt acid lithium of expression.Compare with common cobalt acid lithium,, load performance and charge-discharge performance are improved owing to can suppress cobalt stripping in electrolyte.
But, add in the cobalt acid lithium of xenogenesis element, because the xenogenesis element is helpless to cell reaction (discharging and recharging reaction), so the addition that can produce along with these xenogenesis elements increases the problem that battery capacity reduces and efficiency for charge-discharge also reduces that makes.In addition, owing to add the xenogenesis element crystallinity is reduced, so also can produce the problem that thermal stability reduces and load performance also reduces.And, also leave the space that much will improve for the efficiency for charge-discharge performance.
Summary of the invention
Therefore, the object of the present invention is to provide and a kind ofly can not reduce battery capacity and efficiency for charge-discharge, and can improve the active material for anode of Li-ion secondary battery and the manufacture method thereof of thermal stability, high rate performance and charge-discharge performance.
Purpose of the present invention is achieved through the following technical solutions: a kind of active material for anode of Li-ion secondary battery, described positive active material are with general formula [LiCo
1-xM
xO
2(M=Ti, Zr)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, in described cobalt compound, by coprecipitated titanium and the zirconium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, and the addition of zirconium is 0.01mol%～3mol% with respect to the amount of cobalt.Its manufacture method, comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium and zirconium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of zirconium is 0.01mol%～3mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
A kind of active material for anode of Li-ion secondary battery, described positive active material are with general formula [LiCo
1-xM
xO
2(M=Ti, V, Nb)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, in described cobalt compound, by coprecipitated titanium and vanadium, the Niobium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, and the addition of Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt.Its manufacture method, comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium and vanadium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, Niobium, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, the addition of Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
A kind of active material for anode of Li-ion secondary battery, described positive active material are with general formula [LiCo
1-xM
xO
2(M=Ti, Zr, V, Nb)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carry out mol ratio as the cobalt compound in cobalt source and lithium compound as the lithium source, in described cobalt compound, by coprecipitated titanium, zirconium, vanadium and the Niobium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, and the addition of zirconium, vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt.Its manufacture method, comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, zirconium, vanadium and Niobium, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, zirconium, the addition of vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
More than every kind of described cobalt compound be cobalt carbonate or cobalt hydroxide or hydroxy cobalt oxide.And described cobalt acid lithium compound, near not phase transformation charging capacity 125mAh/g.
Have with general formula [LiCo as positive active material
1-xM
xO
2(M=Ti, Zr, V, Nb)] the cobalt acid lithium of hexagonal crystal system of expression, this cobalt acid lithium is by to being synthesized into as the cobalt compound in cobalt source and lithium compound as the lithium source, in cobalt compound, titanium, zirconium, vanadium, Niobium have been added by co-precipitation, wherein the addition of titanium is that the addition of zirconium, vanadium and Niobium is more than the 0.01mol%, below the 1.5mol% with respect to the amount of cobalt more than the 0.01mol%, below the 1.0mol%.
Here, if when cobalt compounds such as carbonate synthesis cobalt, cobalt hydroxide, hydroxy cobalt oxide, add titanium, zirconium, vanadium or Niobium by co-precipitation, the situation of titanium, zirconium, vanadium or Niobium of adding during then with the oxide that contains lithium and cobalt at sintering is compared, and can add a spot of titanium, zirconium, vanadium or Niobium equably on the limit face of cobalt acid lithium.In the case,, can not supervene the reduction of capacity as can be known when synthesizing cobalt compound, can obtain tangible performance improvement effect if the amount of adding with respect to cobalt by co-precipitation is the titanium of 0.01mol%～1.0mol%.
In addition, generally, when mixed sintering cobalt source and lithium source, added the cobalt acid lithium of titanium, zirconium, vanadium or the Niobium of 1.50mol%, near charging capacity 125mAh/g, produced phase transformation, and can not improve security performance, charge-discharge performance etc.But except adding titanium, also the cobalt acid lithium of zirconium, vanadium or Niobium has been added in co-precipitation simultaneously, does not produce phase transformation near charging capacity 125mAh/g, and has improved thermal stability (security performance), charge-discharge performance etc.
Think this be because: except adding titanium, when also zirconium, vanadium or Niobium have been added in co-precipitation simultaneously, can take into account generation and suppress the phase transformation inhibition effect of effect, interpolation zirconium, vanadium or Niobium generation, the effect of promotion crystal growth, can improve characteristic significantly by these synergies by the stripping of interpolation titanium generation cobalt.
And, in order to obtain positive active material as described above, having co-precipitation operation, mixed processes and sintering circuit gets final product, above-mentioned co-precipitation operation, add titanium, zirconium, vanadium or Niobium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by crossing precipitation, wherein, with respect to the amount of cobalt, wherein the addition of titanium is 0.01mol%～1.0mol%, and the addition of zirconium, vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt; Above-mentioned mixed processes forms mixture to being mixed with second composition that is made of the lithium compound that becomes the lithium source by first composition that becomes behind the cobalt compound that titanium, zirconium, vanadium and Niobium co-precipitation are obtained; Described sintering circuit is carried out sintering to this mixture.
In addition, in the present invention, for a kind of Heat stability is good being provided, demonstrating higher fail safe, and charge has improved, has suppressed the lithium rechargeable battery of deterioration when charging is preserved, and it is characterized in that using specific positive active material.Thereby,, can use material known in the past for negative material, diaphragm material, nonaqueous electrolyte material, binder material.
In the present invention, use with general formula [LiCo as positive active material
1-xM
xO
2(M=Ti, Zr, V, Nb)] the cobalt acid lithium of hexagonal crystal system of expression, this cobalt acid lithium is by to being synthesized into as the cobalt compound in cobalt source and lithium compound as the lithium source, in cobalt compound, titanium, zirconium, vanadium, Niobium have been added by co-precipitation, wherein the addition of titanium is 0.01mol%～1.0mol%, and the addition of zirconium, vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt.In view of the above,, can obtain can not making battery capacity and efficiency for charge-discharge to reduce, the lithium rechargeable battery that thermal stability, high rate performance and charge-discharge performance have improved by adding a spot of titanium.
The advantage that the present invention has: can not reduce battery capacity and efficiency for charge-discharge, and can improve thermal stability, high rate performance and charge-discharge performance.
Description of drawings
Fig. 1 is the anodal charging and discharging curve of expression is produced flex point by phase transformation a schematic diagram;
Fig. 2 is the schematic diagram that the anodal charging and discharging curve of expression does not produce flex point;
Embodiment
1. Zheng Ji making
(1) added the making of the cobalt acid lithium of Ti and Zr
At first, at cobaltous sulfate (CoSO
4) add the titanyl sulfate [TiOSO of ormal weight in the solution
4] and zirconium sulfate [Zr (SO
4)
2] afterwards, by adding NaOH and ammoniacal liquor, and at synthetic cobalt hydroxide [Co (OH)
2] time make titanium (Ti) and zirconium (Zr) co-precipitation.Then, by making them carry out the cobaltosic oxide (Co that pyrolysis has obtained as the interpolation of the initial feed in cobalt source titanium and zirconium
3O
4).
Then, at the initial feed lithium carbonate (Li that has prepared as the lithium source
2CO
3) after, making the mol ratio of lithium and cobalt with the scale weighing is 1: 1.Then, these are mixed with mortar, again with the mixture that obtains in air with 900 ℃ of sintering 20 hours, and synthesize the sinter of the cobalt acid lithium powder that has added titanium and zirconium on the surface.Afterwards, it is 12 μ m that synthetic sinter is ground into average grain diameter, and as positive active material.
Here, will be with respect to the cobalt amount, the addition of titanium is 0.50mol%, the addition of zirconium is that the synthetic positive active material of the mode of 0.01mol% is as positive active material a1, to be that the synthetic positive active material of the mode of 0.50mol% is as positive active material a2 with the addition of zirconium, to be that the synthetic positive active material of the mode of 1.00mol% is as positive active material a3 with the addition of zirconium, to be with the addition of zirconium the synthetic positive active material of the mode of 1.20mol% as positive active material a4, will be that the synthetic positive active material of the mode of 1.50mol% is as positive active material a5 with the addition of zirconium.
In addition, the addition that will be 0.50mol%, zirconium with the addition of titanium be the synthetic positive active material of the mode of 3mol% as positive active material a6, will not add the synthetic positive active material of zirconium as positive active material x1.In addition, the addition of titanium, zirconium is by ICP (Inductively CoupledPlasma; Plasma emission spectrum) analyzes the value that obtains.
(2) added the making of the cobalt acid lithium of Ti and V and Nb
At first, at cobaltous sulfate (CoSO
4) add the titanyl sulfate [TiOSO of ormal weight in the solution
4] and vanadic sulfate [VOSO
4] and Niobium acid sodium [Na
3NbO
4] afterwards, by adding NaOH and ammoniacal liquor, and at synthetic cobalt hydroxide [Co (OH)
2] time make titanium (Ti) and vanadium (V) and Niobium (Nb) co-precipitation.Then, by making them carry out the cobaltosic oxide (Co that pyrolysis has obtained as the interpolation of the initial feed in cobalt source titanium, vanadium, Niobium
3O
4).
Then, at the initial feed lithium carbonate (Li that has prepared as the lithium source
2CO
3) after, making the mol ratio of lithium and cobalt with the scale weighing is 1: 1.Then, these are mixed with mortar, again with the mixture that obtains in air with 900 ℃ of sintering 20 hours, and synthesize the sinter of the cobalt acid lithium powder that has added titanium, vanadium, Niobium on the surface.Afterwards, it is 12 μ m that synthetic sinter is ground into average grain diameter, and as positive active material.
Here, will be with respect to the cobalt amount, the addition of titanium is 0.50mol%, the addition of vanadium and Niobium respectively is that the synthetic positive active material of the mode of 0.01mol% is as positive active material b1, to respectively be that the synthetic positive active material of the mode of 0.50mol% is as positive active material b2 with the addition of vanadium and Niobium, to respectively be that the synthetic positive active material of the mode of 1.00mol% is as positive active material b3 with the addition of vanadium and Niobium, to respectively be with the addition of vanadium and Niobium the synthetic positive active material of the mode of 1.20mol% as positive active material b4, will be with the addition of vanadium and Niobium for respectively being that the synthetic positive active material of the mode of 1.50mol% is as positive active material b5.
In addition, will be that the addition of 0.50mol%, vanadium and Niobium respectively is that the synthetic positive active material of the mode of 3mol% is as positive active material b6 with the addition of titanium.In addition, the addition of titanium, vanadium and Niobium is by ICP (Inductively Coupled Plasma; Plasma emission spectrum) analyzes the value that obtains.
(3) added the making of the cobalt acid lithium of Ti, Zr, V and Nb
At first, at cobaltous sulfate (CoSO
4) add the titanyl sulfate [TiOSO of ormal weight in the solution
4], zirconium sulfate [Zr (SO
4)
2], vanadic sulfate [VOSO
4] and Niobium acid sodium [Na
3NbO
4] afterwards, by adding NaOH and ammoniacal liquor, and at synthetic cobalt hydroxide [Co (OH)
2] time make titanium (Ti), zirconium (Zr), vanadium (V) and Niobium (Nb) co-precipitation.Then, by making them carry out the cobaltosic oxide (Co that pyrolysis has obtained as the interpolation of the initial feed in cobalt source titanium, zirconium, vanadium, Niobium
3O
4).
Then, at the initial feed lithium carbonate (Li that has prepared as the lithium source
2CO
3) after, making the mol ratio of lithium and cobalt with the scale weighing is 1: 1.Then, these are mixed with mortar, again with the mixture that obtains in air with 900 ℃ of sintering 20 hours, and synthesize the sinter of the cobalt acid lithium powder that has added titanium, zirconium, vanadium, Niobium on the surface.Afterwards, it is 12 μ m that synthetic sinter is ground into average grain diameter, and as positive active material.
Here, will be with respect to the cobalt amount, the addition of titanium be the addition of 0.50mol%, zirconium be 1.00mol%, vanadium and Niobium addition respectively for the synthetic positive active material of the mode of 0.01mol% as positive active material c1.In addition, under the addition of titanium and the zirconium situation identical with above-mentioned c1, to respectively be that the synthetic positive active material of the mode of 0.50mol% is as positive active material c2 with the addition of vanadium and Niobium, to respectively be that the synthetic positive active material of the mode of 1.00mol% is as positive active material c3 with the addition of vanadium and Niobium, to respectively be with the addition of vanadium and Niobium the synthetic positive active material of the mode of 1.20mol% as positive active material c4, will be with the addition of vanadium and Niobium for respectively being that the synthetic positive active material of the mode of 1.50mol% is as positive active material c5.And under the addition of titanium and the zirconium situation identical with above-mentioned c1, the addition of vanadium and Niobium respectively is that the synthetic positive active material of the mode of 3mol% is as positive active material c6.
In addition, the addition of titanium, zirconium, vanadium and Niobium is by ICP (Inductively Coupled Plasma; Plasma emission spectrum) analyzes the value that obtains.
Then, use each positive active material a1～a6, the x1, b1～b6, the c1～c6 that as above make like that, be 85 mass parts, be 10 mass parts, be that the mode of 5 mass parts is mixed with these a few positive active materials, make anode mixture as Kynoar (PVdF) powder of binding agent as the carbon dust of conductive agent.Then, with the anode mixture that obtains mix with N-methyl pyrrolidone (NMP) form anode sizing agent after, on the two sides of the positive electrode collector (aluminium foil) of thickness 20 μ m, be coated with this anode sizing agent, and on the two sides of positive electrode collector, form active material layer by scraping the skill in using a kitchen knife in cookery.After making it drying, use compressing roller that it is rolled to the thickness of regulation, cut into the size of regulation again, make anodal respectively.
Then, make the lithium metal relative with each positive pole of as above making to, it is immersed in the organic electrolyte, this organic electrolyte is to dissolve LiPF being mixed in the mixed solvent that constitutes by ethylene carbonate (EC), diethyl carbonate (DEC) equal-volume
6, and make LiPF
6For 1mol/l modulates, and the potential change when depicting with the 300mA constant current charge is tried to achieve charging curve.So, in the positive pole that uses positive active material x1, as shown in Figure 1, near the charging curve the 125mAh/g, find the flex point H that produces by phase transformation.On the other hand, in the positive pole that uses positive active material a1～a6, b1～b6 and c1～c6, as shown in Figure 2, the flex point that near the charging curve the 125mAh/g, does not have discovery to produce by phase transformation.
2. the making of negative pole
In addition, after mixing with native graphite powder 95 mass parts, as Kynoar (PVdF) powder 5 mass parts of binding agent, it is mixed as cathode size with N-methyl pyrrolidone (NMP).Afterwards, by scraping the skill in using a kitchen knife in cookery cathode size that obtains is coated on the two sides of the negative electrode collector that thickness is 18 μ m (Copper Foil), and on the two sides of negative electrode collector, forms active material layer.After making its drying, utilize compressing roller to roll, cut into given size again, make negative pole to the thickness of regulation.
3. the making of lithium rechargeable battery
Then, use aforesaid positive pole and negative pole, and between them, sandwich after the barrier film that is made of polyethylene system perforated membrane is piled up, utilize up-coiler to be wound into helical form, made the spiral electrode group.Afterwards, inject the organic electrolyte that is modulated in Package casing, wherein, this organic electrolyte is by dissolve LiPF in the mixed solvent that is mixed formation by ethylene carbonate (EC), diethyl carbonate (DEC) equal-volume
6, and make LiPF
6For 1mol/l modulates, be 18mm, highly be the lithium rechargeable battery of 1600mAh for 65mm and design capacity thereby made diameter respectively.[A1～A6, B1～B6, C1～C6 and X1]
Here, to use the lithium rechargeable battery of positive active material a1 as battery A1, to use the lithium rechargeable battery of positive active material a2 as battery A2, to use the lithium rechargeable battery of positive active material a3 as battery A3, to use the lithium rechargeable battery of positive active material a4 as battery A4, as battery A5, will use the lithium rechargeable battery of positive active material a6 the lithium rechargeable battery that used positive active material a5 as battery A6.In addition, to use the lithium rechargeable battery of positive active material b1 as battery B1, to use the lithium rechargeable battery of positive active material b2 as battery B2, to use the lithium rechargeable battery of positive active material b3 as battery B3, to use the lithium rechargeable battery of positive active material b4 as battery B4, as battery B5, will use the lithium rechargeable battery of positive active material b6 the lithium rechargeable battery that used positive active material b5 as battery B6.
In addition, to use the lithium rechargeable battery of positive active material c1 as battery C1, to use the lithium rechargeable battery of positive active material c2 as battery C2, to use the lithium rechargeable battery of positive active material c3 as battery C3, to use the lithium rechargeable battery of positive active material c4 as battery C4, as battery C5, will use the lithium rechargeable battery of positive active material c6 the lithium rechargeable battery that used positive active material c5 as battery C6.In addition, will use the lithium rechargeable battery of positive active material x1 as battery X1.
4. the mensuration of battery behavior
(1)
The anodal heat analysis (mensuration of DSC heating beginning temperature) of charging then, is used these batteries A1～A6, B1～B6, C1～C6 and X1 respectively, and under 25 ℃ temperature environment, with the charging current of 100mA, constant current charge to cell voltage reaches 4.2V.Then, decompose these batteries in drying box, take out positive pole, clean with dimethyl carbonate, vacuumize obtains test film again.To the ethylene carbonate of these test films 4mg interpolation 1mg, afterwards, in the battery unit of atmosphere lower sealing at aluminum of argon gas.Then, these batteries are put into differential scanning calorimeter (DSC), heat up, measure the temperature (DSC heating beginning temperature) that each test film begins to generate heat self, obtained the result shown in the table 1 described as follows with the programming rate of 5 ℃/min.
(2) initial capacity
In addition, use these batteries A1～A6, B1～B6, C1～C6 and X1 respectively, under 25 ℃ temperature environment, charging current with 1600mA, after constant current charge to voltage reaches 4.2V, carry out constant voltage charge, reach 30mA until stopping electric current with the constant voltage of 4.2V.Thereafter, with the discharging current of 1600mA, be discharged to cell voltage and reach 2.75V, the discharge capacity according to trying to achieve the 1st circulation discharge time has obtained the result shown in the table 1 described as follows.
(3) high rate performance
Equally, use these batteries A1～A6, B1～B6, C1～C6 and X1 respectively, under 25 ℃ temperature environment, charging current with 1600mA, after constant current charge to voltage reaches 4.2V, carry out constant voltage charge, reach 30mA until stopping electric current with the constant voltage of 4.2V., with the discharging current of 1600mA, be discharged to cell voltage reach 2.75V, with its discharging and recharging as the 1st circulation thereafter.Then,, after constant current charge to voltage reaches 4.2V, carry out constant voltage charge, reach 30mA until stopping electric current with the constant voltage of 4.2V with the charging current of 1600mA., with the discharging current of 4800mA, be discharged to cell voltage reach 2.75V, with its discharging and recharging as the 2nd circulation thereafter.Then, try to achieve the ratio (%) of the discharge capacity of the 2nd circulation as high rate performance (%), obtained the result shown in the table 1 described as follows with respect to the discharge capacity of the 1st circulation.
(4) 25 ℃ of charge and discharge cycles capacity sustainment rates
In addition, use these batteries A1～A6, B1～B6, C1～C6 and X1 respectively, under 25 ℃ temperature environment, charging current with 1600mA, after constant current charge to voltage reaches 4.2V, carry out constant voltage charge, reach 30mA until stopping electric current with the constant voltage of 4.2V., with the discharging current of 1600mA, be discharged to cell voltage reach 2.75V, with its discharging and recharging as the 1st circulation thereafter.Then, carry out such charge and discharge cycles repeatedly 300 times, try to achieve the ratio (%) of the discharge capacity of the 300th circulation as 25 ℃ of charge and discharge cycles capacity sustainment rates (%), obtained the result shown in the table 1 described as follows with respect to the discharge capacity of the 1st circulation.
(5) 60 ℃ of charge and discharge cycles capacity sustainment rates
In addition, use these batteries A1～A6, B1～B6, C1～C6 and X1 respectively, under 60 ℃ temperature environment, charging current with 1600mA, after constant current charge to voltage reaches 4.2V, carry out constant voltage charge, reach 30mA until stopping electric current with the constant voltage of 4.2V., with the discharging current of 1600mA, be discharged to cell voltage reach 2.75V, with its discharging and recharging as the 1st circulation thereafter.Then, carry out such charge and discharge cycles repeatedly 300 times, try to achieve the ratio (%) of the discharge capacity of the 300th circulation as 60 ℃ of charge and discharge cycles capacity sustainment rates (%), obtained the result shown in the table 1 described as follows with respect to the discharge capacity of the 1st circulation.
(6) phase transformation has or not
In addition, when these batteries A1～A6, B1～B6, C1～C6 and X1 are discharged and recharged, test the situation that near the charging and discharging curve charging capacity is 125mAh/g, to have found the flex point that produces by phase transformation and be judged to be phase transformation, will find not that the situation of flex point is judged to be no phase transformation that its result is illustrated in the following table 1.
| Battery variety | Ti adds (mol%) | Zr addition (mol%) | V addition (mol%) | Nb addition (mol%) | DSC heating beginning temperature (℃) | Initial capacity (mAh) | High rate performance (%) | 25 ℃ of charge and discharge cycles capacity sustainment rates (%) | 60 ℃ of charge and discharge cycles capacity sustainment rates (%) | Phase transformation has or not |
| ??X1 | ??0.50 | Do not have | Do not have | Do not have | ??179 | ??1630 | ??95 | ??93 | ??78 | Have |
| ??A1 | ??0.50 | ??0.01 | Do not have | Do not have | ??184 | ??1633 | ??95 | ??96 | ??81 | Do not have |
| ??A2 | ??0.50 | ??0.50 | Do not have | Do not have | ??186 | ??1634 | ??96 | ??96 | ??82 | Do not have |
| ??A3 | ??0.50 | ??1.00 | Do not have | Do not have | ??189 | ??1629 | ??96 | ??97 | ??82 | Do not have |
| ??A4 | ??0.50 | ??1.20 | Do not have | Do not have | ??189 | ??1627 | ??96 | ??97 | ??83 | Do not have |
| ??A5 | ??0.50 | ??1.50 | Do not have | Do not have | ??191 | ??1630 | ??95 | ??97 | ??82 | Do not have |
| ??A6 | ??0.50 | ??3.00 | Do not have | Do not have | ??190 | ??1600 | ??92 | ??97 | ??81 | Do not have |
| ??B1 | ??0.50 | Do not have | ??0.01 | ??0.01 | ??188 | ??1630 | ??98 | ??94 | ??82 | Do not have |
| ??B2 | ??0.50 | Do not have | ??0.50 | ??0.50 | ??192 | ??1628 | ??98 | ??94 | ??85 | Do not have |
| ??B3 | ??0.50 | Do not have | ??1.00 | ??1.00 | ??193 | ??1629 | ??98 | ??93 | ??85 | Do not have |
| ??B4 | ??0.50 | Do not have | ??1.20 | ??1.20 | ??193 | ??1628 | ??98 | ??94 | ??84 | Do not have |
| ??B5 | ??0.50 | Do not have | ??1.50 | ??1.50 | ??194 | ??1626 | ??98 | ??94 | ??83 | Do not have |
| ??B6 | ??0.50 | Do not have | ??3.00 | ??3.00 | ??195 | ??1597 | ??98 | ??94 | ??82 | Do not have |
| ??C1 | ??0.50 | ??1.00 | ??0.01 | ??0.01 | ??196 | ??1634 | ??95 | ??98 | ??84 | Do not have |
| ??C2 | ??0.50 | ??1.00 | ??0.50 | ??0.50 | ??196 | ??1630 | ??95 | ??98 | ??85 | Do not have |
| ??C3 | ??0.50 | ??1.00 | ??1.00 | ??1.00 | ??198 | ??1632 | ??96 | ??97 | ??85 | Do not have |
| ??C4 | ??0.50 | ??1.00 | ??1.20 | ??1.20 | ??199 | ??1627 | ??96 | ??98 | ??85 | Do not have |
| ??C5 | ??0.50 | ??1.00 | ??1.50 | ??1.50 | ??198 | ??1625 | ??96 | ??98 | ??85 | Do not have |
| ??C6 | ??0.50 | ??1.00 | ??3.00 | ??3.00 | ??199 | ??1606 | ??96 | ??97 | ??85 | Do not have |
Can clearly see from the result of above-mentioned table 1: is 0.01mol% when above at the addition of zirconium (Zr) with respect to the amount of cobalt, and DSC heating beginning temperature rises, and the capacity sustainment rate after 25 ℃, 60 ℃ the circulation 300 times obviously improves.Estimate this be because: is 0.01mol% when above at the addition of zirconium with respect to the amount of cobalt, and charging capacity is that near the phase transformation the 125mAh/g is suppressed, and it is stable that crystal structure becomes.And, through near charging capacity is 125mAh/g, carrying out the X-ray diffraction evaluation, can confirm that battery X1 goes up the positive active material x1 that uses and fades to hexagonal crystal system from hexagonal crystal system mutually through monoclinic system.
But among the positive active material a1～a6 that uses in battery A1～A6, as shown in Figure 2, as can be known: no phase transformation still is a hexagonal crystal system.In addition, when the addition of zirconium was 3.00mol% with respect to the amount of cobalt, initial capacity reduced, and multiplying power property also reduces.Consider for these, can assert preferably with the addition of zirconium with respect to the amount of cobalt be limited in more than the 0.01mol%, below the 1.5mol%.
Similarly, find: at the addition of vanadium and Niobium is 0.01mol% when above, and the heating of DSC begins temperature and rises.In addition, also find: the capacity sustainment rate after 60 ℃ the circulation 300 times obviously improves.Estimate this be because: is 0.01mol% when above at the addition of vanadium and Niobium with respect to the amount of cobalt, and charging capacity is that near the phase transformation of 125mAh/g is suppressed, and it is stable that crystal structure becomes.And, through near charging capacity is 125mAh/g, carrying out the X-ray diffraction evaluation, can confirm not have phase transformation, still be hexagonal crystal system.In addition, when the addition of vanadium and Niobium was 3.00mol% with respect to the amount of cobalt, initial capacity reduced, and multiplying power property also reduces.Consider for these, can assert preferably the addition of vanadium and Niobium is limited in 0.01mol%～1.5mol% with respect to the amount of cobalt.
Relative therewith, find: in Ti (0.5mol%), added Zr (1mol%) and vanadium and Niobium (among 0.01～3mol%) both battery C1～C6 of positive active material c1～c6, DSC heating beginning temperature uprises, anodal thermal stability raising using.But, the change that the amount of vanadium and Niobium improves, initial capacity reduces.
In addition, clearly find from the result of above-mentioned table 1: among the battery A3 that uses the positive active material a3 that only adds Ti (0.5mol%) and Zr (1mol%), do not add vanadium and Niobium, DSC heating beginning temperature step-down, anodal thermal stability reduction.Can assert preferably the addition of vanadium and Niobium is limited in 0.01mol%～1.5mol% with respect to the amount of cobalt.
In addition, in the above-described embodiment, after when synthesizing cobalt hydroxide, making titanium, zirconium, vanadium and Niobium co-precipitation, be illustrated by making them carry out the example that pyrolysis obtained as the interpolation of the initial feed in cobalt source the cobaltosic oxide of titanium, zirconium, vanadium and Niobium, but also can: after when synthesis of hydroxy cobalt oxide or cobalt carbonate or cobalt oxalate, making titanium, zirconium, vanadium and Niobium co-precipitation, obtained as the interpolation of the initial feed in cobalt source the cobaltosic oxide of titanium, zirconium, vanadium and Niobium by making them carry out pyrolysis.
Claims (8)
1. active material for anode of Li-ion secondary battery, it is characterized in that: described positive active material is with general formula [LiCo
1-xM
xO
2(M=Ti, Zr)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, in described cobalt compound, by coprecipitated titanium and the zirconium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, and the addition of zirconium is 0.01mol%～3mol% with respect to the amount of cobalt.
2. active material for anode of Li-ion secondary battery, it is characterized in that: described positive active material is with general formula [LiCo
1-xM
xO
2(M=Ti, V, Nb)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, in described cobalt compound, by coprecipitated titanium and vanadium, the Niobium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, and the addition of Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt.
3. active material for anode of Li-ion secondary battery, it is characterized in that: described positive active material is with general formula [LiCo
1-xM
xO
2(M=Ti, Zr, V, Nb)] the cobalt acid lithium compound of hexagonal crystal system of expression, described cobalt acid lithium is by being to mix at 1: 1 to obtain to carry out mol ratio as the cobalt compound in cobalt source and lithium compound as the lithium source, in described cobalt compound, by coprecipitated titanium, zirconium, vanadium and the Niobium of having added, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, and the addition of zirconium, vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt.
4. according to any described active material for anode of Li-ion secondary battery in the claim 1 to 3, it is characterized in that: described cobalt compound is cobalt carbonate or cobalt hydroxide or hydroxy cobalt oxide.
5. according to any described active material for anode of Li-ion secondary battery in the claim 1 to 3, it is characterized in that: described cobalt acid lithium compound, near not phase transformation charging capacity 125mAh/g.
6. according to the manufacture method of the described active material for anode of Li-ion secondary battery of claim 1, it is characterized in that: comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium and zirconium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of zirconium is 0.01mol%～3mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
7. according to the manufacture method of the described active material for anode of Li-ion secondary battery of claim 2, it is characterized in that: comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium and vanadium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, Niobium, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, the addition of Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
8. according to the manufacture method of the described active material for anode of Li-ion secondary battery of claim 3, it is characterized in that: comprise the co-precipitation operation, mixed processes and sintering circuit, described co-precipitation operation, add titanium at the initial stage cobalt compound that is used for thermal decomposition and becomes the cobalt compound in cobalt source by co-precipitation, zirconium, vanadium and Niobium, wherein the addition of titanium is 0.01mol%～1mol% with respect to the amount of cobalt, the addition of vanadium is 0.01mol%～1.5mol% with respect to the amount of cobalt, zirconium, the addition of vanadium and Niobium is 0.01mol%～1.5mol% with respect to the amount of cobalt, described mixed processes is by being to mix at 1: 1 to obtain to carrying out as the cobalt compound in cobalt source and lithium compound as the lithium source with mol ratio, again with the mixture that obtains in air with 880～920 ℃ of temperature sintering 18～20 hours.
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