CN100420088C - Lithium ion secondary cell with nickel-base anode active material and producing method thereof - Google Patents
Lithium ion secondary cell with nickel-base anode active material and producing method thereof Download PDFInfo
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- CN100420088C CN100420088C CNB2004100885459A CN200410088545A CN100420088C CN 100420088 C CN100420088 C CN 100420088C CN B2004100885459 A CNB2004100885459 A CN B2004100885459A CN 200410088545 A CN200410088545 A CN 200410088545A CN 100420088 C CN100420088 C CN 100420088C
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000006183 anode active material Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000011267 electrode slurry Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011149 active material Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229910016123 LiNi1-x-y-zCoxAlyMnzO2 Inorganic materials 0.000 abstract 1
- 239000012267 brine Substances 0.000 abstract 1
- 239000005486 organic electrolyte Substances 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 (EMC) Chemical compound 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 230000000505 pernicious effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 239000010405 anode material Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
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- 239000011265 semifinished product Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a lithium ion secondary battery which uses modification LiNiO 2 for a positive pole, graphitized carbon materials are used for a negative pole, non-aqueous organic electrolyte is used, wherein the positive pole comprises base materials of positive pole materials and a coating layer at the surface of base material granules, the base materials are LiNi1-x-y-zCoxAlyMnzO2, x, y and z satisfy 0<x<0.4, 0</=y</=0.3, 0</=z<0.5, and materials of the coating layer are oxides or fast ion conductive glass. A method for preparing the lithium ion secondary battery comprises: (1) the brine solution of nickel salt, cobalt salt and manganese salt is used for preparing a mixed hydroxide of a precursor; (2) the hydroxide of the precursor is sintered with a compound containing lithium, and the base materials of the granular positive pole materials are manufactured; (3) the base material granules of positive pole active materials are coated; (4) liquid lithium ion battery technology is adopted to manufacture the lithium ion secondary battery. The lithium ion secondary battery of the present invention has fine cycle performance and coating technology performance.
Description
Technical field
The present invention relates to lithium rechargeable battery, especially relate to Ni-based lithium-contained composite oxide and make lithium rechargeable battery of positive electrode active materials and preparation method thereof.
Background technology
Lithium rechargeable battery is a rechargeable nonaqueous electrolytic battery, its operating voltage height, energy density is big, life-span is long, self-discharge rate is low, memory-less effect, and be of value to environment, be mobile communication and portable electric appts, as the main power source of notebook computer, camcorder, digital camera and PDA (personal digital assistant) etc.At present, business-like lithium ion battery is made negative pole with the graphitized carbon material of inserting lithium, with cobalt acid lithium (LiCoO
2) positive electrode active materials work positive pole, with nonaqueous electrolyte such as LiPF
6Ethylene carbonate (EC) and the mixed solvent solution of methyl ethyl carbonate (EMC) make electrolyte.For lithium ion battery, use LiCoO
2Make positive electrode, the electrode good processability, the specific capacity height has very good cycle performance; But its shortcoming is the cobalt resource poorness, and cobalt compound costs an arm and a leg, and uses LiCoO
2Make positive electrode cost height.Exploitation can replace LiCoO
2Various positive electrode active materials, be the most popular research topic from last century since the nineties always.Wherein, with the lithium-contained composite oxide LiNi of nickel as main component
1-xCo
xO
2, because energy density height (170-180mAh/g) is hopeful most.Although through further modification, as add other metallic elements M, make product LiNi
1-x-yCo
xM
yO
2Structural stability, thermal stability and energy keep performance all to improve a lot, but as industrialized positive electrode active materials, still have major defect, reason is to exist bigger pernicious interaction (Arora P. between the electrolyte of these materials and battery, White R.E., Doyle M., J.Electrochem.Soc.1998.145 (10): 3647-3667).
Recently, people coat surface of positive electrode active material and discover, LiNi
1-xCo
xO
2Lip-deep MgO nano coating can suppress it with the pernicious interaction between electrolyte, and significantly improves electrochemistry cycle performance (Electro-chemicaland Solid state Letters, 3 (3) 128-130 (2000)).But coat the problem that often runs in the research at the positive electrode particle surface and be: the clad material poorly conductive that (1) has often makes the positive electrode active materials specific capacity after the coating that greater loss is arranged; (2) clad material that has has conductivity preferably, but makes the slurrying and the coating processing characteristics severe exacerbation of positive electrode after applying.Chinese patent application CN1414650A, CN1280397A, CN1346158A, CN1346160A, CN1357932A, CN13666363A, CN1379488A, CN1416189A etc. have proposed multiple positive electrode active materials with coating layer, but all do not propose the solution of these problems.
Summary of the invention
An object of the present invention is to provide a kind of lithium rechargeable battery, it has high specific capacity and good processability, and this battery is with modification LiNiO
2Be positive pole, graphitized carbon material is a negative pole, uses non-water organic bath, and described positive pole comprises the positive electrode base material and at the coating layer on substrate particle surface, described base material is LiNi
1-x-y-zCo
xAl
yMn
zO
2, wherein x, y, z satisfy 0＜x＜0.4,0≤y≤0.3,0≤z＜0.5 respectively, and described coating layer material is oxide or fast ion conduction glass, and described oxide comprises MgO, ZnO, SiO
2, B
2O
3, Al
2O
3, TiO
2, ZrO
2, SnO
2, V
2O
5, MnO
2, described fast ion conduction glass comprises Li
2OB
2O
3, Li
2OAl
2O
3B
2O
3, Li
2OSiO
2, Li
2OAl
2O
3SiO
2, LiFLi
3PO
4, LiFAlPO
4, LiFLi
2SiO
3, X (0.6Li
2S0.4SiS
2) (1-X) Li
3PO
4, X (0.6Li
2S0.4SiS
2) (1-X) Li
3BO
3, 0＜X＜1 wherein.
Another object of the present invention provides a kind of method for preparing lithium rechargeable battery of the present invention, and it has overcome the problem that coating processes exists in the prior art, and this method may further comprise the steps:
(1) with the saline solution of nickel salt, cobalt salt and manganese salt, with the alkali lye co-precipitation, preparation has the presoma mixed hydroxides of α-crystal formation or beta-crystal, and the saline solution of described nickel salt, cobalt salt and manganese salt comprises any in nitrate, sulfate, the acetate.The alkali lye that coprecipitation reaction is used is sodium hydrate aqueous solution or NaOH/ammonium hydroxide mixed alkali liquor, the total concentration of the slaine of coprecipitation reaction is the 2-4 mol, the temperature of reactor is maintained at about 50 ℃, the pH value of coprecipitation reaction remains on 11-12, the coprecipitation reaction product is washed repeatedly up to neutrality, gets the spherical Ni doped Co (OH) of class after the drying
2Powder.
(2), make graininess positive electrode base material LiNi with described presoma hydroxide and lithium-containing compound sintering
1-x-y-zCo
xAl
yMn
zO
2, wherein x, y, z satisfy 0＜x＜0.4,0≤y≤0.3,0≤z＜0.5 respectively.Lithium-containing compound is lithia, lithium carbonate or monohydrate lithium hydroxide.The reaction temperature of sintering reaction is 600 ℃～900 ℃, is preferably 650 ℃-850 ℃, and in the described sintering reaction, lithium-containing compound is to described Ni doped Co (OH)
2Stoichiometric proportion be: 1～1.20: 1, be preferably 1.02～1.08: 1.
(3) with coating layer material solution and assistance coating layer material difference or the synthetic positive electrode active materials substrate particle of mixing coating above-mentioned steps.Coating layer material is oxide or fast ion conduction glass, and described oxide comprises MgO, ZnO, SiO
2, B
2O
3, Al
2O
3, TiO
2, ZrO
2, SnO
2, V
2O
5, MnO
2, described fast ion conduction glass comprises Li
2OB2O
3, Li
2OAl
2O
3B
2O
3, Li
2OSiO
2, Li
2OAl
2O
3SiO
2, LiFLi
3PO
4, LiFAlPO
4, LiFLi
2SiO
3, X (0.6Li
2S0.4SiS
2) (1-X) Li
3PO
4, X (0.6Li
2S0.4SiS
2) (1-X) Li
3BO
3, 0＜X＜1 wherein.
The assistance coating layer material is a polymer solution, when adopting the aqueous solution to apply, described polymer solution is a water-soluble polymer solution, comprise polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), water soluble starch, low molecular weight polyacrylamide, PTFE emulsion, SBR emulsion, when adopting oil phase to apply, described polymer solution is PVDF solution, VDF/HFP copolymer solution.
(4) adopt liquid lithium ionic cell technology to make lithium rechargeable battery.If wherein in the conductive agent of the electrode slurry of positive electrode, add conductive carbon black, then better effects if.Conductive carbon black is SuperP, VXC-72, VXC-72R or BP2000.The particle size of conductive carbon black is 35 μ m, and consumption is the 3-5% of positive electrode active materials base material weight.
Lithium rechargeable battery according to the present invention's preparation has good cycle performance and coating process performance.
Description of drawings
Fig. 1 is the charge discharge characteristic schematic diagram of material before applying;
Fig. 2 is the charge discharge characteristic schematic diagram that applies the back material;
Fig. 3 is material " 053048 " rectangular cell charge-discharge performance (1-10 cycle) schematic diagram before applying;
Fig. 4 applies back material " 053048 " rectangular cell charge-discharge performance (1-10 cycle) schematic diagram.
Embodiment
Lithium rechargeable battery of the present invention, belong to rechargeable nonaqueous electrolytic battery, it makes negative active core-shell material with graphitized carbon material, can make the positive electrode active materials base material by the reversible composite oxides of moving out and inserting with lithium ion, mixed carbonic acid ester solution with lithium salts is an electrolyte, the LiNi of described positive electrode active materials base material for obtaining by softening synthetic method
1-x-y-zCo
xAl
yMn
zO
2, 0＜x＜0.4,0≤y≤0.3,0≤z＜0.5 wherein.
But the negative active core-shell material of this lithium rechargeable battery can be graphite graphitized carbon material and difficult graphitized carbon material, is preferably graphite.Nonaqueous electrolyte is to be made of solvent and the lithium salts that is dissolved in the solvent, as described solvent, for example can use ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate ring-type and linear carbonate such as (EMC), methyl acetate, fatty acid esters such as ethyl propionate, and r-butyrolactone, 1,2-dimethoxy ethane (DME), oxolane, 1, the 3-dioxolanes, acetamide, non-proton organic solvents such as dimethyl formamide, they can use or mix use separately, the mixture of wherein preferred cyclic carbonate and linear carbonate.
Described lithium salts for example can be used LiClO
4, LiBF
4, LiPF
6, LiSCN, LiCF
3SO
3, Li (CF
3SO
2)
2, LiAsF
6, LiN (CF
3SO
2)
2Deng, preferred LiPF
6
Described nonaqueous electrolyte, preferred LiPF
6Be dissolved in the solution in EC, EMC and DMC or EC and the DMC mixed solvent, wherein LiPF
6Concentration be preferably 0.5-2mol/L, 0.8-1.5mol/L preferably.
Described positive electrode active materials base material LiNi
1-x-y-zCo
xAl
yMn
zO
2(0＜x＜0.4,0≤y≤0.3,0≤z＜0.5) prepares by the softening synthetic method of learning.At first, with the sulfate solution of nickel, cobalt, aluminium and the manganese of certain mol proportion with " NaOH/NH
4OH " the alkali lye co-precipitation, obtain presoma hydroxide.Then by certain molar ratio with it with single water hydroxide ground and mixed.Then be placed in the kiln 650-800 ℃ roasting 16-24 hour, gained black product is for having and LiCoO
2The single-phase LiNi of identical layer structure
1-x-y-zCo
xAl
yMn
zO
2, its specific capacity is greater than 170mAh/g.
Described LiNi
1-x-y-zCo
xAl
yMn
zO
2The positive electrode active materials substrate particle is carried out the surface by the following method and coated: at first, the preparation coating layer material is the Li of 1-20 weight %
2OB
2O
3Coating solution (A liquid), preparation is worked in coordination with the water-soluble polymer solution that applies with coating liquid again, is 250,000 the PEO aqueous solution (B liquid) as molecular weight.Then with the above-mentioned LiNi of 100g drying
1-x-y-zCo
xAl
yMn
zO
2Pour in the 800ml large beaker of built-in 50ml A liquid, do not stop to stir it.Coating layer material is preferably 0.05-5% to the weight ratio that is coated with the positive electrode active materials substrate particle, is preferably 0.1%-2%, decides on the kind of coating layer material.Then add an amount of collaborative coating solution (B liquid) slowly.Collaborative coating solution B liquid is to the weight ratio of the active material based material particle of positive pole, and the 0.05%-2% scope is preferably in the 0.1-1% scope more fortunately.The mixture that will be added with A liquid B liquid at last is under constantly stirring, and heated volatile falls moisture, treat that water is almost evaporated fully after, will apply afterproduct and be moved in baking oven in 110-120 ℃ of following heat treatment 10-20 hour.Next further heat treatment, first section heat treatment temperature is 300 ℃, and heat treatment time is 2 hours, and second section heat treatment temperature is between 500-700 ℃, and the heat treatment time scope is 4-10 hour.Product after the heat treatment is the positive electrode active materials that the present invention applied through grinding 500 mesh sieves.Above-mentioned coating layer material can be following oxide: MgO, ZnO, B
2O
3, Al
2O
3, SiO
2, TiO
2, ZrO
2, SnO
2, V
2O
5, and MnO
2Deng.Also can be following super ionic conducting glass: Li
2OAl
2O
3SiO
2, Li
2OSiO
2, LiFLi
3PO
4, LiFAlPO
4, LiFLi
2SiO
2, X (0.6Li
2S0.4SiS
2) (1-X) Li
3PO
4And X (0.6Li
2S0.4SiS
2) (1-X) Li
3BO
3Deng, wherein, 0＜X＜1.
As for the lithium ion battery manufacture method, can adopt existing liquid lithium ionic cell production technology and equipment, both can make rectangular lithium ion battery, also can make cylindrical battery.The related description of embodiments of the invention square shaped battery is suitable for cylindrical battery too.
Below in conjunction with specific embodiment the present invention is made information description.But, should not be construed as the present invention and only limit to these embodiment.
Embodiment 1
PEO (M=25 ten thousand) aqueous solution (B liquid) 100ml of preparation 2% concentration is stand-by earlier.Then, preparation 100ml is to include 1 (weight) %H
3BO
3Li (OH) H of meter
2OH
3BO
3The aqueous solution (A liquid), wherein Li (OH) H
2O/H
3BO
3=1: 2 (mol ratios).Take by weighing dry back and cross 500 purpose positive electrode active materials base material Li
1.07Ni
0.75Co
0.01Al
0.10Mn
0.05O
2Particle 100g, its input is filled in the beaker of 50ml A liquid, stir it, add 100ml B liquid again, stirred again 1 hour.Then, heating up under agitation slowly allows water evaporates, treat that water is done after, it is moved on in the baking oven 110-120 ℃ of heating 10 hours.After this, product is heat-treated, first section heat treatment temperature is 300 ℃, heat treatment time 2 hours, and second section heat treatment temperature is 650 ℃, heat treatment time is 10 hours, through handling like this, promptly gets the positive electrode active materials after the present invention applies.
Fig. 1 is the charge discharge characteristic schematic diagram of material before applying.Fig. 2 is the charge discharge characteristic schematic diagram that applies the back material.Fig. 1 and Fig. 2 difference are little, even the specific volume value of material is than applying the aforementioned slightly end a bit after the coating of being tried to achieve by Fig. 2, but this is not crucial.
Embodiment 2
Used positive electrode base material is Li
1.07Ni
0.75Co
0.01Al
0.10Mn
0.05O
2, its particle surface method for coating is identical with embodiment 1, and difference just B liquid is that molecular weight is the polyvinyl alcohol of 2 (weight) % concentration of 100,000.
The pole piece manufacturing of battery, Integration Assembly And Checkout method are with embodiment 1, owing to work in coordination with clad anode material with A liquid B liquid, anode sizing agent is not dry, good fluidity, and the pole piece manufacturing does not have hell and high water.Made battery also shows to have good charge-discharge performance.Its charging and discharging curve is extremely similar to accompanying drawing 4.
Used positive electrode base material is with embodiment 1, and its method for coating is also identical, difference be used A liquid be the aluminum nitrate solution of 2 (weight) %.For obtaining Al
2O
3The nanometer coating layer after positive electrode particle to be coated drops in the 500ml A liquid 1000g, under constantly stirring, must dropwise add the ammoniacal liquor (concentrated ammonia liquor: water=1: 4) of 5 times of dilutions.
The manufacture method of electrode slice and battery is with embodiment 1.The gained battery also has good cycle performance, and its charging and discharging curve is extremely similar to accompanying drawing 4.
500 order positive electrode active materials 2000g of the coating that so makes and Changsha Xing Cheng graphite with 4 meters long small-scale lithium ion cell coating machines coating positive/negative plates, are made " 053048 " square bar housing battery, and detailed process is as follows:
(1) positive plate manufacturing
With the Li after the above-mentioned coating
1.07Ni
0.75Co
0.01Al
0.10Mn
0.05O
2Positive electrode powder, conductive agent VXC-72R (Cabot company product) and as the Kynoar (PVDF) of bonding agent weight ratio batching by 92: 5: 3, during slurrying, earlier PVDF is dissolved in 65 parts of dehydration N-methyl pyrrolidones (N-MP), and then positive electrode powder and VXC-72R electrically conductive graphite added in the PVDF solution slowly, stirred 5-6 hour, and can get anode sizing agent.Then, with above-mentioned 4 grow small-sized coating sizing-agent machine with the slurry double spread on the thick collector body aluminium foil of 20 μ m, after drying and the roll-in, make positive plate.If with B liquid and the active powder of the collaborative clad anode of A liquid, then slurry is not dry, solvent is volatile, is difficult to coating and makes positive plate.
(2) negative plate manufacturing
With the weight ratio blanking of Changsha Xing Cheng graphite, bonding agent SBR emulsion and sanlose (CMC) by 93: 5: 2.During slurrying, earlier CMC is dissolved in 100 parts of water, treats molten finishing, under agitation, add 5 parts of SBR emulsions and add the graphite cathode powder gradually, high degree of agitation 4 hours promptly gets cathode size.With above-mentioned 4 meters long small-sized coating machines, the cathode size two sided coatings on 12 μ m Copper Foils, is promptly got negative plate after doing.
(3) battery assembling
Above-mentioned positive and negative plate and diaphragm paper are complied with " 053048 " size that battery requires, cut, the spot welding lug, then, reel, adorn shell, laser spot welding cover plate, drying, fluid injection, preliminary filling successively, seal, can make the box hat battery of model for " 053048 " with usual technology.
(4) battery testing
The semi-finished product battery that drying is good injects the organic bath of 2.4g, after placing 2h, test with certain charge and discharge system, charge and discharge system is: the 1st step is with 0.05C mA electric current constant current charge 2h, the 2nd step is with 0.1CmA electric current constant current charge 2h, the 3rd step then with 0.2C mA electric current constant current charge till the 4.5V, the 4th step was then used constant voltage 4.5V instead, and to charge to electric current be 10mA, after leaving standstill 5min, the 5th step again with 0.2C mA electric current constant-current discharge to cut-ff voltage 2.75V, so just finish preliminary filling and change into step, last, with battery seal, get final product to such an extent that model is the finished steel housing battery of " 053048 ".
Then, the battery of finishing preliminary filling and change into is carried out loop test in the following manner: the 1st step, be 4.5V with 0.2C mA electric current constant current charge to voltage earlier, the 2nd the step, be 10mA with 4.5V voltage constant voltage charge to electric current again, leave standstill 5min after, the 3rd step, then with 0.2C mA electric current constant-current discharge to cut-ff voltage 2.75V, circulate the positive electrode active materials Li after can obtaining the present invention and applying by this way 10 times
1.00Ni
0.75Co
0.01Al
0.10Mn
0.05O
2Charge-discharge performance figure, see Fig. 4.
Fig. 3 is the schematic diagram of material " 053048 " rectangular cell charge-discharge performance (1-10 cycle) before applying.Fig. 4 is the schematic diagram that applies back material " 053048 " rectangular cell charge-discharge performance (1-10 cycle).Wherein, reference numerals is 1 expression first charge-discharge curve, uses charging 1 and discharge 1 expression respectively.Reference numerals is the 10th charging and discharging curves of 10 expressions, uses charging 10 and discharge 10 expressions respectively.The charge-discharge performance figure (seeing Fig. 3 and Fig. 4) of positive electrode active materials before and after relatively applying, find to apply the charging and discharging curve region of variation of back positive electrode active materials than narrow and small before applying, that is to say before applying back positive electrode active materials performance applies more stable, this has just proved that also coating layer material can suppress the pernicious interaction of electrolyte and positive electrode, reduce the destruction of electrolyte, thereby improved the cycle performance of positive electrode anodal material structure.
In sum; the above only is a preferred implementation of the present invention; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvement and distortion, for example; with molecular weight is that the polyacrylic acid sodium water solution of 1.5 (weight) % concentration of 10-15 ten thousand is made synergist (B liquid) and also can be received similar effect, and these improvement and distortion also should be considered as falling into protection scope of the present invention.
Claims (14)
1. lithium rechargeable battery, this battery is with modification LiNiO
2Be positive pole, graphitized carbon material is a negative pole, uses non-water organic bath, it is characterized in that: described positive pole comprises the positive electrode base material and at the coating layer on substrate particle surface, described base material is LiNi
1-x-y-zCo
xAl
yMn
zO
2, wherein x, y, z satisfy 0＜x＜0.4,0≤y≤0.3,0≤z＜0.5 respectively, and described coating layer material is a fast ion conduction glass, and described fast ion conduction glass is LiFLi
3PO
4, LiFAlPO
4, LiFLi
2SiO
3, X (0.6Li
2S0.4SiS
2) (1-X) Li
3PO
4Or X (0.6Li
2S0.4SiS
2) (1-X) Li
3BO
3, 0＜X＜1 wherein.
2. the preparation method of a lithium rechargeable battery, described lithium rechargeable battery is with modification LiNiO
2Being positive pole, is negative pole with the graphitized carbon material, uses non-water organic bath, and described positive pole comprises the positive electrode base material and at the coating layer on substrate particle surface, described base material is LiNi
1-x-y-zCo
xAl
yMn
zO
2, wherein x, y, z satisfy 0＜x＜0.4,0≤y≤0.3,0≤z＜0.5 respectively, and described coating layer material is oxide or fast ion conduction glass, the method is characterized in that may further comprise the steps:
(1) with the saline solution of nickel salt, cobalt salt and manganese salt, with the alkali lye co-precipitation, preparation has the presoma mixed hydroxides of α-crystal formation or beta-crystal;
(2), make graininess positive electrode base material with described presoma hydroxide and lithium-containing compound sintering;
(3) coat the solution difference or mix the synthetic positive electrode active materials substrate particle of coating above-mentioned steps with assisting with coating layer material solution, assisting coating solution is polymer solution;
(4) adopt liquid lithium ionic cell technology to make lithium rechargeable battery.
3. according to the preparation method of claim 2, it is characterized in that: described nickel salt, cobalt salt and manganese salt are any in nitrate, sulfate, the acetate.
4. according to the preparation method of claim 2, it is characterized in that: the alkali lye that coprecipitation reaction is used is sodium hydrate aqueous solution or NaOH/ammonium hydroxide mixed alkali liquor.
5. according to the preparation method of claim 2 or 4, it is characterized in that: the total concentration of the nickel salt of coprecipitation reaction, cobalt salt and manganese salt is the 2-4 mol, and the temperature of reactor remains on 40-60 ℃, and the pH value of coprecipitation reaction remains on 11-12.
6. according to the preparation method of claim 2, it is characterized in that: lithium-containing compound is lithia, lithium carbonate or monohydrate lithium hydroxide.
7. according to the preparation method of claim 2 or 6, it is characterized in that: the reaction temperature of sintering reaction is 600 ℃～900 ℃, and in the described sintering reaction, lithium-containing compound to the mol ratio of presoma hydroxide is: 1～1.20: 1.
8. according to the preparation method of claim 2, it is characterized in that: the described oxide as clad material is MgO, B
2O
3, Fe
2O
3, SiO
2, SnO
2, TiO
2Or ZrO
2, described fast ion conduction glass is Li
2OB
2O
3, Li
2OSiO
2, LiFLi
3PO
4, X (0.6Li
2S0.4SiS
2) (1-X) Li
3PO
4, X (0.6Li
2S0.4SiS
2) (1-X) Li
2SiO
3Or X (0.6Li
2S0.4SiS
2) (1-X) Li
3BO
3, 0＜X＜1 wherein.
9. according to the preparation method of claim 2, it is characterized in that: in substrate particle coating step (3),
When adopting the aqueous solution to apply, described polymer solution is a water-soluble polymer solution, be selected from polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), water soluble starch, low molecular weight polyacrylamide, PTFE emulsion or SBR emulsion, when adopting oil phase to apply, described polymer solution is PVDF solution or VDF/HFP copolymer solution.
10. according to the preparation method of claim 2, it is characterized in that: the amount of described coating layer material is 0.05% to 5% of a positive electrode active materials base material weight.
11. the preparation method according to claim 2 or 10 is characterized in that: assisting the consumption of coating solution is 0.05% to 2% of positive electrode active materials base material weight.
12. the preparation method according to claim 2 is characterized in that: in the conductive agent of the electrode slurry of positive electrode active materials, add conductive carbon black.
13. the preparation method according to claim 12 is characterized in that: described conductive carbon black is Super P, VXC-72, VXC-72R or BP2000.
14. according to the preparation method of claim 12, the particle size of described conductive carbon black is 35 μ m, consumption is the 3-5% of positive electrode active materials base material weight.
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