CN101997113A - Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof - Google Patents
Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN101997113A CN101997113A CN200910091243XA CN200910091243A CN101997113A CN 101997113 A CN101997113 A CN 101997113A CN 200910091243X A CN200910091243X A CN 200910091243XA CN 200910091243 A CN200910091243 A CN 200910091243A CN 101997113 A CN101997113 A CN 101997113A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- lithium ion
- multicomponent material
- clad structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000463 material Substances 0.000 title claims abstract description 105
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 238000001556 precipitation Methods 0.000 claims description 39
- 150000004706 metal oxides Chemical class 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 32
- 229910013716 LiNi Inorganic materials 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 12
- 229940078494 nickel acetate Drugs 0.000 claims description 12
- 229940011182 cobalt acetate Drugs 0.000 claims description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 9
- 239000011565 manganese chloride Substances 0.000 claims description 9
- 235000002867 manganese chloride Nutrition 0.000 claims description 9
- 229940099607 manganese chloride Drugs 0.000 claims description 9
- 239000011833 salt mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229960005137 succinic acid Drugs 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical class [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000012958 reprocessing Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000012792 core layer Substances 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 238000002156 mixing Methods 0.000 description 28
- 239000012266 salt solution Substances 0.000 description 26
- 230000014759 maintenance of location Effects 0.000 description 16
- 230000012010 growth Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000035939 shock Effects 0.000 description 9
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- -1 salt ion Chemical class 0.000 description 2
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910013603 LiCo0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 230000010261 cell growth Effects 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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Abstract
The invention discloses a multicomponent material for a lithium ion battery and a preparation method thereof, and particularly relates to a multicomponent material with a multilayer coating structure for a lithium ion battery and a preparation method thereof. The multicomponent material with the multilayer coating structure comprises an inner core and coating layers, wherein both the inner core and the coating layers comprise lithium-containing metallic oxides; and the number n of the coating layers is 1 to 5. The multicomponent material with the multilayer coating structure has a simple preparation process, relatively low cost and high processability; and the lithium ion battery made of the material has a small amount of swelling, high capacity, high high-temperature cyclical stability and high safety.
Description
Technical field
The present invention relates to a kind of lithium ion battery with multicomponent material and preparation method thereof, relate to a kind of lithium ion battery multicomponent material of multilayer clad structure and preparation method thereof specifically;
Background technology
Lithium ion battery in the application of modern society more and more widely is mainly used in fields such as mobile phone, notebook computer, electric tool and electric motor car at present.Along with the increase of lithium ion battery consumption and electric automobile, press for development and have high security, high-energy-density, high power, long circulation life, high environmental protection and cheap lithium ion battery the high capacity lithium ion battery demand.Positive electrode is the performance of decision lithium ion battery and the critical material of price, and studying and use more positive electrode at present has LiCoO
2, LiNiO
2, LiNi
xCo
1-xO
2, LiNi
xCo
yMn
1-x-yO
2, LiMnO
2, LiMn
2O
4, LiFePO
4LiCoO
2Be the lithium electricity positive electrode of commercial applications the earliest, and be still the main positive electrode of present use, this mainly is because its stable performance is synthetic easily; But because the Co resource-constrained, this material price is higher, and certain toxicity is arranged, and has limited its application in some emerging markets.LiNiO
2Capacity height, cost are lower, but the preparation difficulty, there are comparatively serious safety problem in the consistency of material property and poor reproducibility.LiNi
xCo
1-xO
2Can regard LiNiO as
2And LiCoO
2Solid solution, have LiNiO concurrently
2And LiCoO
2Advantage, once it is believed that it is most possibly to replace LiCoO
2Novel anode material, but still have shortcomings such as synthetic difficulty, fail safe be relatively poor, combination property haves much room for improvement.Stratiform LiMnO
2Cost is low, initial capacity is high, but has the shortcoming of cycle performance difference.
Because layer structure helps reversibly embedding/deviate from Li
+So, wish to develop cheaper, environmental protection more, the better layer structure positive electrode of performance.In recent years, stratiform LiNi
xCo
yMn
1-x-yO
2Research attracted attention by the people, integrated LiNiO
2, LiCoO
2, LiMnO
2Wait the advantage of each material: higher capacity, cyclical stability, high rate capability, thermal stability also have good cyclical stability under higher temperature preferably, are the anode material for lithium-ion batteries that has very much exploitation to be worth.
LiNi
xCo
yMn
1-x-yO
2Raising specific capacity along with Ni content in the solid solution increases to some extent, as LiNi
0.8Co
0.1Mn
0.1O
2Reversible capacity can reach 190mAh/g, considerably beyond LiCoO
2(about 145mAh/g), but the cycle performance of material, security performance descend thereupon.Therefore, such nickel-rich positive pole material is subjected to some restriction in its actual application facet:
At first, the violent phase transformation of crystal structure can take place and follow the variation of volume in nickel-rich positive pole material in the charge/discharge process that repeats, can cause the local collapse in crystal layer space, cause lithium ion to embed/deviate from and to be caused polarization resistance to increase by obstruction, thereby cause the charge/discharge cycle performance decrease.In order to solve this type of problem, prior art attempts to prepare nickel-rich positive pole material by optimizing synthesis condition, yet it is limited to improve effect.
Secondly, nickel-rich positive pole material is storing or cycle period, has a large amount of gases and produces, and causes the battery bulging.Prior art is added excessive lithium source, and is heat-treated in oxygen atmosphere in order to form good crystal structure in producing the nickel-rich positive pole material process.Consequently, Li
2CO
3Or lithium salts such as LiOH remains between the particle as reaction residue, and LiOH absorbs airborne CO
2Also can be converted into Li
2CO
3, Li when charging
2CO
3Decompose or generation CO with the electrolyte reaction
2Gas may cause the generation of cell expansion and the deterioration of high temperature safety.
It is Li that patent application CN1778003 has proposed composition formula
y(Ni
xCo
1-2xMn
x) O
2, 0.025≤x≤0.5 wherein, nickel content is lower, and cycle performance is better, and security performance improves to some extent, but specific capacity is lower; It is Li that patent application CN101300696 has then proposed composition formula
x(Ni
1-a-b(Ni
1/2Mn
1/2)
aCo
bA
k)
yO
2, high nickel content material, its specific capacity of 0.4≤Ni≤0.7,0.1≤Co≤0.4,0.05≤Mn≤0.6 increase, but the low nickel material of cycle performance, security performance decreases.
Summary of the invention
A kind of lithium ion battery multicomponent material of multilayer clad structure and preparation method thereof provided by the invention, this material has excellent comprehensive performances, adopt the capacity of lithium ion battery height of this material, the battery bulging is little, high temperature circulation is stable, safe, and material preparation process is simple, cost is cheap relatively.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of lithium ion battery comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and kernel and coating layer include the metal oxide that contains lithium, and coating number of plies n is 1-5, is preferably 1-3.
Described coating layer gross thickness is 1 with the ratio of interior nuclear radius: 200-10: 1, be preferably 1: 10-5: 1.
The particle meso-position radius that described kernel and coating layer are formed is 5-30 μ m, and tap density is 1.5-3.0g/cm
3
The metal oxide that contains lithium in the described kernel comprises LiNi
xCo
yMn
zG
wO
2Wherein, 0.4≤x≤1.0,0≤y+z≤0.6, x+y+z+w=1, G are one or more elements among Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, Ta, Mo, the W.
The metal oxide that contains lithium in the described coating layer comprises LiNi
aCo
bMn
cL
uO
2, 0≤a≤0.6,0.4≤b+c≤1.0 wherein, a+b+c+u=1, L are one or more elements among Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, Ta, Mo, the W.
The degree of Ni is less than kernel in the described outermost coating layer, and the degree that is preferably Ni in the described coating layer increases with n and successively successively decreases from inside to outside, i.e. the multicomponent material of gradient type multilayer clad structure.
A kind of lithium ion battery is by the positive pole of the multicomponent material of described multilayer clad structure; Negative pole; Barrier film; Compositions such as electrolyte.
A kind of lithium ion battery comprises the steps: with the preparation method of the multicomponent material of multilayer clad structure
(1) be that nickel cobalt manganese salt-mixture, complexing agent, the precipitation reagent of x: y: z: w is mixed with the aqueous solution respectively with nickel, cobalt, manganese, G mol ratio, and stream injects reactor, make kernel presoma slurries with the crystallization coprecipitation.This process should be under non-oxidizing atmosphere protection, carries out under 40-80 ℃, and the pH value is 8-13.The salt of G is selected from a kind of or wherein several mixture of solubility chlorination salt, sulfate, nitrate, acetate, citrate, alkoxide.
(2) be that nickel cobalt manganese salt-mixture, complexing agent, the precipitation reagent of a: b: c: u is mixed with the aqueous solution respectively with nickel, cobalt, manganese, L mol ratio, and flow and inject the reactor that contains kernel presoma slurries, make the multicomponent material presoma slurries that coat number of plies n=1 with the crystallization coprecipitation.This process should be under non-oxidizing atmosphere protection, carries out under 40-80 ℃, and the pH value is 8-13, nickel salt, cobalt salt, the same step of manganese salt (1) in the nickel cobalt manganese salt-mixture.The salt of L is a kind of or wherein several mixture of solubility chlorination salt, sulfate, nitrate, acetate, citrate, alkoxide.
(3) n＞1 o'clock, nickel, cobalt, manganese, the L salt-mixture of complexing agent, precipitation reagent and different compositions are mixed with the aqueous solution respectively, and stream injects the reactor that contains n-1 layer presoma slurries, make the multicomponent material presoma slurries that the n layer coats with the crystallization coprecipitation, this process should be under the non-oxidizing atmosphere protection, carry out under 40-80 ℃, the pH value is 8-13, washing after filtration,, reprocessing, reprocessing is that oven dry is or/and calcining, wherein calcining heat is 300-600 ℃, obtains the hydroxide or the oxide multicomponent material presoma of the spherical multilayer clad structure of n＞1; The salt of L is a kind of or wherein several mixture of solubility chlorination salt, sulfate, nitrate, acetate, citrate, alkoxide.
(4) with the multicomponent material presoma and the lithium source batch mixing of n layer clad structure, in mixing tank, mix, in oxidizing atmosphere, under 600-1200 ℃, preferred 850-1000 ℃, sintering 1-40h, preferred 7-20h through broken, obtains the multicomponent material of spherical multilayer clad structure.
Nickel salt is a kind of or wherein several mixture in nickelous sulfate, nickel chloride, nickel nitrate, nickel acetate, the nickel acetate in the middle nickel cobalt manganese salt-mixture in described step (1) and/or (2) and/or (3); Cobalt salt is a kind of or wherein several mixture in cobaltous sulfate, cobalt chloride, cobalt nitrate, the cobalt acetate; Manganese salt is a kind of or wherein several mixture in manganese sulfate, manganese chloride, manganese nitrate, the manganese acetate.
Complexing agent is a kind of or wherein several mixture in EDTA, ammoniacal liquor, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium citrate, ethylenediamine, acetate, ammonium acetate, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid, the malonic acid in described step (1) and/or (2) and/or (3); The ratio of this complexing agent and the total salt of metal can determine that the mol ratio of complexing agent and the total salt of metal is 0.2-5.0 according to complexation equilibrium principle or actual needs.Precipitation reagent is a kind of or wherein several mixture in ammoniacal liquor, NaOH, potassium hydroxide, the lithium hydroxide, and control precipitation reagent and the total salt mol ratio of metal are 1.5-2.5.
The lithium source is a kind of or wherein several mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, the lithium hydrogen phosphate in the described step (4), is preferably a kind of or wherein several mixture in lithium carbonate, lithium hydroxide and the lithium nitrate.
The multicomponent material of gained multilayer clad structure is become pole piece with carbon black, Kynoar (PVDF) by 94%: 3%: 3% weight ratio batching and slurry, negative pole adopts Delanium, the centre add membrane coil around and fluid injection after, be processed into 053048 shell with square aluminum battery; The chemical property of test battery and security performance.(according to lithium ion battery standard GB/T18287-2000:C
5Be rated capacity, expression with 5 hour rates be discharged to final voltage the electric weight that should provide, unit is Ah or mAh; 1C
5The A charge and discharge cycles is meant under 20 ± 5 ℃ of conditions, with 1C
5A charges to 4.2V, changes constant voltage charge to charging current≤0.01C
5A is again with 1C
5A is discharged to 2.75V, forms 1 cycle, repeats 1C afterwards again
5A charge/discharge process.1C
5A high temperature charge and discharge cycles is meant under 60 ± 2 ℃ of conditions, with 1C
5A charges to 4.2V, changes constant voltage charge to charging current≤0.01C
5A is again with 1C
5A is discharged to 2.75V, forms 1 cycle, repeats 1C afterwards again
5A charge/discharge process.Specific discharge capacity is meant 0.2C
5When A discharges and recharges, the capacity that every gram positive electrode discharges under the discharge condition, unit is mAh/g; 85 ℃ of high temperature storage cell thickness rates of change are meant under 20 ± 5 ℃ of conditions, with 0.2C
5A charges to 4.2V, changes constant voltage charge to charging current≤0.01C
5A is again with 1C
5A is discharged to 2.75V, forms 1 cycle, carries out 1C afterwards
5The A charge when battery is circulated to the charged state of the 3rd circulation, is taken off its original depth of battery measurement, it is placed 4 hours under 85 ± 5 ℃ of conditions again, measures its thickness, the thickness change of counting cell; 150 ℃ of interior thermal shocks of hot case are meant under 20 ± 5 ℃ of conditions, with 0.2C
5A charges to 4.2V, changes constant voltage charge to charging current≤0.01C
5A is again with 1C
5A is discharged to 2.75V, forms 1 cycle, carries out 1C afterwards
5The A charge when battery is circulated to the charged state of the 3rd circulation, is taken off battery and is placed in the baking oven, rises to 150 ℃ with the programming rate of 5 ℃/min, investigates battery 150 ℃ of times of blast down.)
The principle of the inventive method is: carry out complexing by adopting complexing agent and metal ion, make the concentration of the total salt ion of metal of the free state that discharges in the reaction system be controlled at a suitable level, as total salt ion in the free metal of this suitable concn level and OH
-When ionic reaction generates sediment, make sediment can form uniform spherical body or class spherical; With the presoma that obtains is nuclear, and stream adds salting liquid, complexing agent, the precipitation reagent of different formulations, can on the spherical surface of this nuclear, deposit the coating layer that makes new advances, can realize the coating of one deck, obtain the polynary presoma of multilayer clad structure to multilayer by such mode; This presoma again with lithium source mixed sintering, finally obtain the multicomponent material of the spherical multilayer clad structure of sphere or class.
The present invention has following advantage:
1. the multicomponent material of multilayer clad structure of the present invention from the performance of material, has taken into full account the characteristic of nickel, cobalt, manganese and other element, and is rational in infrastructure.Kernel adopts nickelic prescription, can bring into play the height ratio capacity advantage of material; Coating layer adopts lower nickel prescription, can improve the high temperature cyclic performance and the security performance of material;
2. the multicomponent material good processability of multilayer clad structure of the present invention, it is little to be made into the battery bulging;
3. preparation technology of the present invention is simple, and cost is cheap relatively, is suitable for industrialization.
Description of drawings
Fig. 1 is profile scanning electron microscope (SEM) figure of a kind of lithium ion battery of the present invention with the multicomponent material of multilayer clad structure;
Fig. 2 is profile scanning electron microscope (SEM) figure of another kind of lithium ion battery of the present invention with the multicomponent material of multilayer clad structure;
Fig. 3 is profile scanning electron microscope (SEM) figure of another kind of lithium ion battery of the present invention with the multicomponent material of multilayer clad structure.
Embodiment
To help to understand the present invention by following embodiment and accompanying drawing, but not limit content of the present invention.
The evaluation of material mode of Comparative Examples and embodiment 1-5 is: this material is become pole piece with carbon black, Kynoar (PVDF) by 94%: 3%: 3% weight ratio batching and slurry, negative pole adopts Delanium, the centre add membrane coil around and fluid injection after, be processed into 053048 shell with square aluminum battery; The chemical property of test battery and security performance.
Comparative Examples 1
The nickel sulfate solution of preparation 1mol/L, the complexing agent ammonia spirit of 2.5mol/L, the precipitation reagent sodium hydroxide solution of 5mol/L.In these three kinds of solution reaction vessel that also the stream adding is stirred simultaneously, control liquid feeding speed makes the pH value of solution of reaction system 12 ± 0.5, water bath heating temperature is 60 ℃, and precipitation, overflow are discharged, and filters, washs, dries, obtain ball-shape nickel hydroxide, fully mix with 1: 1.25 mol ratio with lithium hydroxide, under the oxygen atmosphere, 850 ℃ of insulation 7h, naturally after lowering the temperature, pulverize, sieving, obtain black LiNiO
2Powder.
After tested, the meso-position radius of this material is 12 μ m, tap density 2.2g/cm
3, specific discharge capacity is 199mAh/g, normal temperature 1C
545.5%, 60 ℃ of 100 capability retention of A charge and discharge cycles, 1C
517.1%, 85 ± 2 ℃ of 4h high temperature storage of 100 capability retentions of A charge and discharge cycles cell thickness rate of change is that the thermal shock test result in 88.7%, 150 ℃ of hot case is blast in 5 minutes.
Embodiment 1
A kind of lithium ion battery as shown in Figure 1, is nucleocapsid structure with the multicomponent material of multilayer clad structure, comprises kernel and coating layer, and the metal oxide that contains lithium in the kernel is LiNiO
2, the metal oxide that contains lithium in the coating layer is LiNi
0.38Co
0.35Mn
0.27O
2, coating number of plies n is 1.
Coating thickness is 1: 4 with the ratio of nuclear radius.
The particle meso-position radius that kernel and coating layer are formed is 15 μ m, and tap density is 2.5g/cm
3
The preparation method is as follows:
The nickel sulfate solution of preparation 1mol/L, the complexing agent ammonia spirit of 2.5mol/L, the precipitation reagent sodium hydroxide solution of 5mol/L.With these three kinds of solution simultaneously and stream add in the reaction vessel that stirs, control liquid feeding speed makes the pH value of solution of reaction system 12, water bath heating temperature is 60 ℃, precipitates the nature overflow and is discharged in the reaction vessel 2 as kernel.Nickel chloride, cobalt chloride, manganese chloride are obtained the mixing salt solution (2) of 1mol/L according to the ratio dissolving of metal molar than 0.38: 0.35: 0.27, in mixing salt solution (2), ammoniacal liquor, the sodium hydroxide solution reactor 2 that also the stream adding is stirred simultaneously, grow at core surface, with material filtering, washing, oven dry, obtain the polynary presoma of hydroxide that one deck coats after the reaction.This presoma is fully mixed with 1: 1.25 mol ratio with lithium hydroxide, under the air atmosphere, 850 ℃ of insulation 7h.Naturally cooling after pulverizing, sieving, obtains the multicomponent material that one deck coats.
After tested, the meso-position radius of this material is 15 μ m, tap density 2.5g/cm
3, specific discharge capacity is 192mAh/g, normal temperature 1C
590.3%, 60 ℃ of 1C of 100 capability retentions of A charge and discharge cycles
5The cell thickness growth rate is the 40 minutes after-explosions of thermal shock test result in 12.5%, 150 ℃ of hot case behind 78.1%, 85 ± 2 ℃ of high temperature storage 4h of 100 capability retentions of A charge and discharge cycles.
Embodiment 2
A kind of lithium ion battery as shown in Figure 2, comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.8Co
0.1Mn
0.08Mg
0.02O
2, coating layer material comprises the metal oxide that contains lithium, coating the number of plies is that n is 2.
The coating layer gross thickness is 1: 1 with the ratio of nuclear radius.
The meso-position radius that kernel and coating layer are formed is about 13 μ m, and tap density is 2.3g/cm
3
The metal oxide that contains lithium in the coating layer ground floor material is LiNi
0.53Co
0.13Mn
0.32Al
0.01Zn
0.01O
2, the metal oxide that contains lithium in the described coating layer second layer material is LiNi
0.23Co
0.42Mn
0.32Ca
0.03O
2
The preparation method is as follows:
With nickel chloride, cobalt chloride, manganese chloride, magnesium sulfate according to metal molar than 0.8: 0.1: 0.08: the dissolving of 0.02 ratio obtains the mixing salt solution (1) of 1mol/L, the complexing agent ammonium citrate solution of preparation 2mol/L, the mol ratio of complexing agent and the total salt of metal is 0.2; The precipitation reagent potassium hydroxide solution of preparation 2mol/L, control precipitation reagent and the total salt mol ratio of metal are 1.5.In mixing salt solution (1), ammonium citrate, three kinds of solution of potassium hydroxide reactor 1 that also the stream adding is stirred simultaneously, be reflected at N
2Carry out under the atmosphere protection, control liquid feeding speed makes the pH value of solution of reaction system 10, and water bath heating temperature is 40 ℃, and the complexing of metal ion hydrolytic condensation generates precipitation, precipitates the nature overflow and is discharged in the reactor 2;
With nickel chloride, cobalt chloride, manganese chloride, aluminum sulfate, zinc sulfate according to metal molar than 0.53: 0.13: 0.32: the dissolving of 0.01: 0.01 ratio obtains the mixing salt solution (2) of 1mol/L, in mixing salt solution (2), ammonium citrate, the potassium hydroxide solution reactor 2 that also the stream adding is stirred simultaneously, this moment is with the nuclear that is precipitated as of former reactor 1, control reaction temperature is 40 ℃, the pH value is 10, in the spheric granules superficial growth, coat the slurries precipitation through obtaining one deck after the 4h reaction;
With nickel chloride, cobalt chloride, manganese chloride, calcium chloride according to metal molar than 0.23: 0.42: 0.32: the dissolving of 0.03 ratio obtains the mixing salt solution (3) of 1mol/L, make two layers according to one deck method for coating and coat the slurries precipitation, wash, dry, obtain the polynary presoma of hydroxide of two layers of clad structure.With lithium carbonate and polynary presoma mol ratio is 0.525 fully to mix.Place high temperature furnace, in the oxygen atmosphere, at 1000 ℃ of insulation 20h.Grind after the cooling, cross 300 mesh sieves.
The specific capacity of positive electrode is 190mAh/g in the battery, 1C
5100 capability retentions 93% of A charge and discharge cycles, 60 ℃ of circulation 100 all capability retentions 85%, behind 85 ± 2 ℃ of high temperature storage 4h the cell thickness growth rate be the thermal shock test result in 10.3%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Embodiment 3
A kind of lithium ion battery comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.4Co
0.48Mn
0.12O
2, coating layer material comprises the metal oxide that contains lithium, coating number of plies n is 2.
Described coating thickness is 1: 10 with the ratio of nuclear radius.
The meso-position radius that described kernel and coating layer are formed is about 10 μ m, and tap density is 2.2g/cm
3
The metal oxide that contains lithium in the described coating layer ground floor material is LiNi
0.2Co
0.5Mn
0.28Mg
0.02O
2, the metal oxide that contains lithium in the described coating layer second layer material is LiCo
0.56Mn
0.42Sr
0.02O
2
The preparation method is as follows:
Nickel nitrate, cobalt nitrate, manganese chloride are dissolved the mixing salt solution (1) that obtains 2.5mol/L according to the ratio of metal molar than 0.4: 0.48: 0.12, the complexing agent ethylenediamine solution of preparation 5mol/L, the mol ratio of complexing agent and the total salt of metal is 5.0; Each mixed ammonium/alkali solutions (2) of 50% of the precipitation reagent potassium hydroxide of preparation 5mol/L and NaOH, control precipitation reagent and the total salt mol ratio of metal are 2.5.In salting liquid (1), ethylenediamine, (2) three kinds of solution of mixed ammonium/alkali solutions reaction vessel 1 that also the stream adding is stirred simultaneously, be reflected at N
2Carry out under the atmosphere protection, control liquid feeding speed makes the pH value of solution of reaction system 13, and water bath heating temperature is 80 ℃, and the complexing of metal ion hydrolytic condensation generates precipitation, precipitates the nature overflow and is discharged in the reaction vessel 2;
With nickel nitrate, cobalt nitrate, manganese nitrate, magnesium nitrate according to metal molar than 0.20: 0.50: 0.28: the dissolving of 0.02 ratio obtains the mixing salt solution (3) of 2.5mol/L, in mixing salt solution (3), ethylenediamine, mixed ammonium/alkali solutions (2) the solution reactor 2 that also the stream adding is stirred simultaneously, this moment is with the nuclear that is precipitated as of former reactor 1, control reaction temperature is 80 ℃, the pH value is 13, in the spheric granules superficial growth, coat the slurries precipitation through obtaining one deck after the 4h reaction;
Cobalt nitrate, manganese nitrate, strontium nitrate are obtained the mixing salt solution (4) of 2.5mol/L according to the ratio dissolving of metal molar than 0.56: 0.42: 0.02, make two layers according to one deck method for coating and coat the slurries precipitation, wash, dry, obtain the polynary presoma of hydroxide of two layers of clad structure.Is 1 fully to mix with lithium nitrate with mol ratio, places high temperature furnace, under the oxygen atmosphere, at 600 ℃ of insulation 30h.After the cooling through grinding, after 300 mesh sieves.
The specific capacity of positive electrode is 152mAh/g in the battery, 1C
591%, 60 ℃ of circulation of 100 capability retentions of A charge and discharge cycles, 100 all capability retentions 81%; Behind 85 ± 2 ℃ of high temperature storage 4h the cell thickness growth rate be the thermal shock test result in 5.5%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Embodiment 4
A kind of lithium ion battery as shown in Figure 3, comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.9Co
0.05Mn
0.05O
2, coating layer material comprises the metal oxide that contains lithium, coating number of plies n is 3.
Described coating thickness is 5: 1 with the ratio of nuclear radius.
The meso-position radius that described kernel and coating layer are formed is about 20 μ m, and tap density is 2.5g/cm
3
The metal oxide that contains lithium in the described coating layer ground floor material is LiNi
0.6Co
0.22Mn
0.18O
2, the metal oxide that contains lithium in the described coating layer second layer material is LiNi
0.4Co
0.36Mn
0.22B
0.02O
2, the metal oxide that contains lithium in the described coating layer trilaminate material is LiNi
0.2Co
0.36Mn
0.42Al
0.02O
2
The preparation method is as follows:
Is the mixing salt solution (1) that dissolving in 0.9: 0.05: 0.05 obtains 1.5mol/L with nickel acetate, cobalt acetate, manganese acetate according to the metal molar ratio, the complexing agent succinic acid solution of preparation 5mol/L, and the mol ratio of complexing agent and the total salt of metal is 5.0; The precipitation reagent lithium hydroxide solution of preparation 5mol/L, control precipitation reagent and the total salt mol ratio of metal are 2.5.In salting liquid (1), butanedioic acid, three kinds of solution of lithium hydroxide reaction vessel 1 that also the stream adding is stirred simultaneously, be reflected at N
2Carry out under the atmosphere protection, control liquid feeding speed makes the pH value of reaction system solution 8, and water bath heating temperature is 60 ℃, and the complexing of metal ion hydrolytic condensation generates precipitation, precipitates the nature overflow and is discharged in the reaction vessel 2;
Nickel acetate, cobalt acetate, manganese acetate are obtained the mixing salt solution (2) of 1.5mol/L according to the ratio dissolving of metal molar than 0.60: 0.22: 0.18, in mixing salt solution (2), butanedioic acid, the lithium hydroxide solution reactor 2 that also the stream adding is stirred simultaneously, this moment is with the nuclear that is precipitated as of former reactor 1, control reaction temperature is 60 ℃, the pH value is 8, in the spheric granules superficial growth, coat the slurries precipitation through obtaining one deck after the 4h reaction;
With nickel acetate, cobalt acetate, manganese acetate, boric acid according to metal molar than 0.40: 0.36: 0.22: the dissolving of 0.02 ratio obtains the mixing salt solution (3) of 1.5mol/L, make two layers according to one deck method for coating and coat the slurries precipitation, with nickel acetate, cobalt acetate, manganese acetate, aluminium acetate according to metal molar than 0.20: 0.36: 0.42: the dissolving of 0.02 ratio obtains the mixing salt solution (4) of 1.5mol/L, make three layers according to one deck method for coating and coat the slurries precipitation, wash, dry, obtain the polynary presoma of hydroxide of three layers of clad structure.Is 0.5 fully to mix with lithium oxalate with mol ratio, places high temperature furnace, under the oxygen atmosphere, at 900 ℃ of insulation 20h.Grind after the cooling, cross 300 mesh sieves.
The specific capacity of positive electrode is 182mAh/g in the battery, 1C
5Behind 87%, 85 ± 2 ℃ of high temperature storage 4h of 94%, 60 ℃ of 100 capability retention of A charge and discharge cycles circulation 100 all capability retentions the cell thickness growth rate be the thermal shock test result in 7.3%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Embodiment 5
A kind of lithium ion battery comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.8Co
0.1Mn
0.08Y
0.02O
2, coating layer material comprises the metal oxide that contains lithium, coating the number of plies is that n is 5.
Described coating thickness is 10: 1 with the ratio of nuclear radius.
The meso-position radius that described kernel and coating layer are formed is about 30 μ m, and tap density is 3.0g/cm
3
The metal oxide that contains lithium in the described coating layer ground floor material is LiNi
0.6Co
0.3Mn
0.08Sm
0.02O
2, the metal oxide that contains lithium in the described coating layer second layer material is LiNi
0.5Co
0.26Mn
0.22Ti
0.02O
2, the metal oxide that contains lithium in the described coating layer trilaminate material is LiNi
0.4Co
0.26Mn
0.32Zn
0.02O
2, the metal oxide that contains lithium in described coating layer the 4th layer material is LiNi
0.3Co
0.26Mn
0.42Zr
0.02O
2, the metal oxide that contains lithium in the described coating layer layer 5 material is LiNi
0.2Co
0.36Mn
0.42Al
0.02O
2
The preparation method is as follows:
Mixing salt solution is according to above-mentioned each layer component and proportioning preparation, method for coating is with embodiment 4, successively coat, nickel salt, cobalt salt, manganese salt are all nitrate, all the other slaines are respectively: samaric nitrate, Titanium Nitrate, zinc citrate, zirconium nitrate, aluminum sulfate, the polynary presoma of hydroxide of five layers of coating of gained.Preparation multicomponent material method is with embodiment 4, and lithium carbonate is used in the lithium source, and sintering temperature is 850 ℃, and sintering time is 40h.
The specific capacity of positive electrode is 165mAh/g in the battery, 1C
5Behind 85%, 85 ± 2 ℃ of high temperature storage 4h of 96%, 60 ℃ of 100 capability retention of A charge and discharge cycles circulation 100 all capability retentions the cell thickness growth rate be the thermal shock test result in 9.8%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Embodiment 6
A kind of lithium ion battery comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.5Co
0.4Mn
0.1O
2, coating layer material comprises the metal oxide that contains lithium, coating the number of plies is that n is 1.
Described coating thickness is 1: 200 with the ratio of nuclear radius.
The meso-position radius that described kernel and coating layer are formed is about 5 μ m, and tap density is 1.5g/cm
3
The metal oxide that contains lithium in the described coating layer material is LiCo
0.5Mn
0.5O
2
The preparation method is as follows:
Nickelous sulfate, cobalt nitrate, manganese chloride are dissolved the mixing salt solution (1) that obtains 2mol/L according to the ratio of metal molar than 0.5: 0.4: 0.1, the complexing agent EDTA solution of preparation 2mol/L, the mol ratio of complexing agent and the total salt of metal is 0.2; The precipitation reagent lithium hydroxide solution of preparation 5mol/L, control precipitation reagent and the total salt mol ratio of metal are 1.5.In mixing salt solution (1), EDTA, three kinds of solution of lithium hydroxide reaction vessel 1 that also the stream adding is stirred simultaneously, be reflected at N
2Carry out under the atmosphere protection; control liquid feeding speed makes the pH value of solution of reaction system 11; water bath heating temperature is 40 ℃; the complexing of metal ion hydrolytic condensation generates precipitation; the overflow of precipitation nature is discharged in the reaction vessel 2; with cobalt chloride; manganese chloride obtains the mixing salt solution (2) of 1mol/L according to the dissolving of 0.5: 0.5 ratio of mol ratio; with mixing salt solution (2); sodium fluoride; in the ammonia spirit reactor 2 that also the stream adding is stirred simultaneously; grow at core surface; after the reaction with material filtering; washing; oven dry obtains the polynary presoma of surface coated hydroxide.Is 1 fully to mix with lithium nitrate with mol ratio, places high temperature furnace, in the oxygen atmosphere, at 1000 ℃ of insulation 1h.Grind after the cooling, cross 300 mesh sieves.
A kind of lithium ion battery is by the positive pole of the multicomponent material that comprises this multilayer clad structure; Artificial plumbago negative pole; The PP/PE/PP barrier film; With LiPF
6Compositions such as organic electrolyte for conducting salt.The specific capacity of positive electrode is 158mAh/g in the battery, 1C
5Behind 80%, 85 ± 2 ℃ of high temperature storage 4h of 92%, 60 ℃ of 100 capability retention of A charge and discharge cycles circulation 100 all capability retentions the cell thickness growth rate be the thermal shock test result in 7.5%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Embodiment 7
A kind of lithium ion battery comprises kernel and coating layer with the multicomponent material of multilayer clad structure, and the metal oxide that contains lithium in the kernel is LiNi
0.9Co
0.05Mn
0.05O
2, coating layer material comprises the metal oxide that contains lithium, coating the number of plies is that n is 3.
Described coating thickness is 1: 1 with the ratio of nuclear radius.
The meso-position radius that described kernel and coating layer are formed is about 21 μ m, and tap density is 2.6g/cm
3
The metal oxide that contains lithium in the described coating layer ground floor material is LiNi
0.6Co
0.22Mn
0.18O
2, the metal oxide that contains lithium in the described coating layer second layer material is LiNi
0.2Co
0.36Mn
0.42Al
0.02O
2, the metal oxide that contains lithium in the described coating layer trilaminate material is LiNi
0.4Co
0.36Mn
0.22B
0.02O
2
The preparation method is as follows:
Is the mixing salt solution (1) that dissolving in 0.9: 0.05: 0.05 obtains 1.5mol/L with nickel acetate, cobalt acetate, manganese acetate according to the metal molar ratio, the complexing agent succinic acid solution of preparation 5mol/L, and the mol ratio of complexing agent and the total salt of metal is 5.0; The precipitation reagent lithium hydroxide solution of preparation 5mol/L, control precipitation reagent and the total salt mol ratio of metal are 2.5.In salting liquid (1), butanedioic acid, three kinds of solution of lithium hydroxide reaction vessel 1 that also the stream adding is stirred simultaneously, be reflected at N
2Carry out under the atmosphere protection, control liquid feeding speed makes the pH value of solution of reaction system 8, and water bath heating temperature is 60 ℃, and the complexing of metal ion hydrolytic condensation generates precipitation, precipitates the nature overflow and is discharged in the reaction vessel 2;
Nickel acetate, cobalt acetate, manganese acetate are obtained the mixing salt solution (2) of 1.5mol/L according to the ratio dissolving of metal molar than 0.60: 0.22: 0.18, in mixing salt solution (2), butanedioic acid, the sodium bicarbonate solution reactor 2 that also the stream adding is stirred simultaneously, this moment is with the nuclear that is precipitated as of former reactor 1, control reaction temperature is 60 ℃, pH value 8, in the spheric granules superficial growth, coat the slurries precipitation through obtaining one deck after the 4h reaction;
With nickel acetate, cobalt acetate, manganese acetate, aluminium acetate according to metal molar than 0.20: 0.36: 0.42: the dissolving of 0.02 ratio obtains the mixing salt solution (3) of 1.5mol/L, make two layers according to one deck method for coating and coat the slurries precipitation, with nickel acetate, cobalt acetate, manganese acetate, boric acid according to metal molar than 0.40: 0.36: 0.22: the dissolving of 0.02 ratio obtains the mixing salt solution (4) of 1.5mol/L, make three layers according to one deck method for coating and coat the slurries precipitation, washing, and at 300 ℃ of following calcining 5h, the polynary presoma of oxide of three layers of clad structure that obtain coating, is 0.5 fully to mix with lithium oxalate with mol ratio, place high temperature furnace, under the oxygen atmosphere, at 900 ℃ of insulation 20h.Grind after the cooling, cross 300 mesh sieves.
The specific capacity of positive electrode is 180mAh/g in the battery, 1C
5Behind 85%, 85 ± 2 ℃ of high temperature storage 4h of 91%, 60 ℃ of 100 capability retention of A charge and discharge cycles circulation 100 all capability retentions the cell thickness growth rate be the thermal shock test result in 7.9%, 150 ℃ of hot case be do not explode in 60 minutes, not on fire, no leakage.
Except that above embodiment, all the other modifications of carrying out with doctrine of equivalents, interpolation and replacement all should be within claim scopes of the present invention.
Claims (19)
1. the multicomponent material of a lithium ion battery usefulness multilayer clad structure comprises kernel and coating layer, and kernel and coating layer include the metal oxide that contains lithium, and coating number of plies n is 1-5.
2. lithium ion battery according to claim 1 is characterized in that the described coating layer gross thickness and the ratio of interior nuclear radius are 1: 200-10: 1 with the multicomponent material of multilayer clad structure.
3. lithium ion battery according to claim 2 is characterized in that the described coating layer gross thickness and the ratio of interior nuclear radius are 1: 10-5: 1 with the multicomponent material of multilayer clad structure.
4. lithium ion battery according to claim 1 is characterized in that with the multicomponent material of multilayer clad structure the particle meso-position radius that described kernel and coating layer are formed is 5-30 μ m, and tap density is 1.5-3.0g/cm
3
5. lithium ion battery according to claim 1 is characterized in that with the multicomponent material of multilayer clad structure the metal oxide that contains lithium in the described kernel comprises LiNi
xCo
yMn
zG
wO
2, wherein, 0.4≤x≤1.0,0≤y+z≤0.6, x+y+z+w=1, G are one or more elements among Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, Ta, Mo, the W.
6. lithium ion battery according to claim 1 is characterized in that with the multicomponent material of multilayer clad structure the metal oxide that contains lithium in the described coating layer comprises LiNi
aCo
bMn
cL
uO
2, 0≤a≤0.6,0.4≤b+c≤1.0 wherein, a+b+c+u=1, L are one or more elements among Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, Ta, Mo, the W.
7. use the multicomponent material of multilayer clad structure according to any described lithium ion battery in the claim 1,5 or 6, the degree that it is characterized in that Ni in the described outermost coating layer is less than kernel.
8. lithium ion battery according to claim 7 is characterized in that with the multicomponent material of multilayer clad structure the degree of Ni in the described coating layer successively successively decreases from inside to outside with the n increase.
9. lithium ion battery according to claim 1 is characterized in that with the multicomponent material of multilayer clad structure described coating number of plies n is 1-3.
10. the preparation method of the multicomponent material of a lithium ion battery usefulness multilayer clad structure comprises the steps:
(1) be that salt-mixture, complexing agent, the precipitation reagent of x: y: z: w is mixed with the aqueous solution respectively with nickel, cobalt, manganese, G mol ratio, and stream injects reactor, make kernel presoma slurries with the crystallization coprecipitation;
(2) be that salt-mixture, complexing agent, the precipitation reagent of a: b: c: u is mixed with the aqueous solution respectively with nickel, cobalt, manganese, L mol ratio, and flow and inject the reactor that contains kernel presoma slurries, make the multicomponent material presoma slurries that coat number of plies n=1 with the crystallization coprecipitation;
(3) n＞1 o'clock, complexing agent, precipitation reagent and nickel, cobalt, manganese, L salt-mixture are mixed with the aqueous solution respectively, and stream injects the reactor that contains n-1 layer presoma slurries, make the presoma slurries with the crystallization coprecipitation, after filtration, washing, reprocessing, obtain the multicomponent material presoma of the spherical n layer clad structure of n＞1;
(4) multicomponent material presoma and the lithium source with n layer clad structure mixes, and in oxidizing atmosphere, under 600-1200 ℃, sintering 1-40h through broken, obtains the multicomponent material of spherical multilayer clad structure.
11. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure reprocessing is that oven dry is or/and calcining in the described step (3).
12. lithium ion battery according to claim 10, is characterized in that nickel salt in described step (1) and/or (2) and/or (3) the nickel cobalt manganese salt-mixture is a kind of or wherein several mixture in nickelous sulfate, nickel chloride, nickel nitrate, nickel acetate, the nickel acetate with the preparation method of the multicomponent material of multilayer clad structure; Cobalt salt is a kind of or wherein several mixture in cobaltous sulfate, cobalt chloride, cobalt nitrate, the cobalt acetate; Manganese salt is a kind of or wherein several mixture in manganese sulfate, manganese chloride, manganese nitrate, the manganese acetate.
13. lithium ion battery according to claim 10, is characterized in that described step (1) and/or (2) and/or (3) process should carry out with the preparation method of the multicomponent material of multilayer clad structure under the non-oxidizing atmosphere protection, the pH value is 8-13.
14. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure the salt of G in the described step (1) is a kind of or wherein several mixture of solubility chlorination salt, sulfate, nitrate, acetate, citrate, alkoxide; The salt of L is a kind of or wherein several mixture of solubility chlorination salt, sulfate, nitrate, acetate, citrate, alkoxide in described step (2) and/or (3).
15. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure the middle complexing agent in described step (1) and/or (2) and/or (3) is a kind of or wherein several mixture in EDTA, ammoniacal liquor, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium citrate, ethylenediamine, acetate, ammonium acetate, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid, the malonic acid.
16. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure the middle precipitation reagent in described step (1) and/or (2) and/or (3) is a kind of or wherein several mixture in ammoniacal liquor, NaOH, potassium hydroxide, the lithium hydroxide.
17. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure the middle lithium source of described step (4) is a kind of or wherein several mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, the lithium hydrogen phosphate.
18. lithium ion battery according to claim 10 is characterized in that with the preparation method of the multicomponent material of multilayer clad structure sintering temperature is 850-1000 ℃ in the described step (4), sintering time is 7-20h.
19. a lithium ion battery is characterized in that comprising the positive pole of the multicomponent material that contains the described multilayer clad structure of claim 1; Negative pole; Barrier film; Electrolyte.
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