WO2024153145A1 - Positive electrode material and battery comprising same - Google Patents
Positive electrode material and battery comprising same Download PDFInfo
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- WO2024153145A1 WO2024153145A1 PCT/CN2024/072850 CN2024072850W WO2024153145A1 WO 2024153145 A1 WO2024153145 A1 WO 2024153145A1 CN 2024072850 W CN2024072850 W CN 2024072850W WO 2024153145 A1 WO2024153145 A1 WO 2024153145A1
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- WIPO (PCT)
- Prior art keywords
- positive electrode
- electrode material
- battery
- mah
- molar ratio
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 114
- 230000002441 reversible effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 170
- 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 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000005056 compaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000007599 discharging Methods 0.000 abstract description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 94
- 229910013553 LiNO Inorganic materials 0.000 description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 36
- 229910052760 oxygen Inorganic materials 0.000 description 36
- 239000001301 oxygen Substances 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000011777 magnesium Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000012298 atmosphere Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- 239000011572 manganese Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 9
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- 229910013733 LiCo Inorganic materials 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 102100027368 Histone H1.3 Human genes 0.000 description 2
- 101001009450 Homo sapiens Histone H1.3 Proteins 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 206010000060 Abdominal distension Diseases 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012278 LiCo0.98Al0.01Mg0.01O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 208000024330 bloating Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Definitions
- the present application belongs to the field of battery technology, and specifically relates to a positive electrode material and a battery containing the positive electrode material.
- Lithium-ion batteries are widely used in various portable electronic products, transportation vehicles, energy storage devices and other fields due to their high energy density and good cycle performance.
- the most widely used is LiCoO 2 with R-3m phase structure, because it has high compaction density, good rate performance and cycle performance.
- commercial LiCoO 2 is developing towards high voltage (>4.5V vs.Li + /Li).
- high voltage >4.5V vs.Li + /Li
- LiCoO 2 will undergo severe phase changes, such as the O3 to H1-3 phase change near 4.55V, and the H1-3 to O1 phase change at higher voltages.
- This irreversible phase change makes the structure of the positive electrode material extremely unstable at high voltages, and the crystal structure undergoes severe c-axis contraction, causing the material particles to rupture or even break, thereby leading to cycle failure.
- the purpose of the present application is to provide a positive electrode material and a battery containing the positive electrode material.
- the positive electrode material has a high capacity, extremely high rate performance and good cycle performance at a charging cut-off voltage of ⁇ 4.65V, which can avoid the risk of oxidative decomposition of the electrolyte caused by further increasing the charging cut-off voltage and improve the cycle life of the whole battery.
- a positive electrode material the chemical formula of the positive electrode material is Li ax Na x Co 1-z1-z2 M 1 z1 M 2 z2 O 2 , wherein 0 ⁇ x ⁇ 0.1, 0.8 ⁇ a ⁇ 1, 0 ⁇ z1 ⁇ 0.07, 0 ⁇ z2 ⁇ 0.07, 0.001 ⁇ z1+z2 ⁇ 0.07, M1 is at least one of Al, Mg, Mn, and Ni, and M2 is at least one of Ti, Zr, B, P, Y, La, Te, Nb, and W;
- the positive electrode material satisfies: m1>m2;
- m1 is the molar content ratio of Li/Na of the positive electrode material before charge and discharge
- m2 is the molar content ratio of Li/Na after the positive electrode material is discharged to 3.0V at a rate of 0.1C.
- the molar content ratio of Li/Na of the positive electrode material is a-x/x.
- m2 is the molar content ratio of Li/Na of the positive electrode material after being assembled into a lithium-ion battery and discharged to 3.0V at a rate of 0.1C, the battery is disassembled, and the discharged positive electrode material is tested.
- x is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08 or 0.09.
- a is 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99.
- z1+z2 is 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, or 0.06.
- the median particle size of the positive electrode material is 3-20 ⁇ m.
- the positive electrode material can avoid the risk of increasing the internal resistance and bloating of the battery due to a long lithium ion migration path by selecting such a median particle size.
- the specific surface area of the positive electrode material is 0.1 to 1.0 m 2 /g. If the specific surface area of the positive electrode material is too small, poor rate performance will result, while if the specific surface area of the positive electrode material is too large, increased electrolyte consumption of the battery using the positive electrode material will result.
- the positive electrode material of the present application can obtain better rate performance and can avoid excessive consumption of electrolyte during the charge and discharge process of the battery.
- the positive electrode material has a polycrystalline or single crystal morphology.
- the crystal phase structure of the positive electrode material is a P63mc phase structure.
- the positive electrode material has a high capacity, extremely high rate performance, and good cycle performance.
- the extremely high rate performance means that it still has a high capacity at a high rate, which can be described by the ratio of the capacity at a high rate to the capacity at a low rate.
- Good cycle performance can be reflected by the ratio of the capacity after multiple cycles to the initial capacity, that is, the capacity retention rate.
- each repeating unit of the positive electrode material has a layered structure in which two transition metal oxygen layers and lithium oxygen layers are alternately arranged (i.e., a layered structure periodically arranged in the manner of transition metal oxygen layer 1-lithium oxygen layer 1-transition metal oxygen layer 2-lithium oxygen layer 2), and the transition metal atoms and lithium atoms occupy octahedral sites respectively.
- Each repeating unit of conventional lithium cobalt oxide has a layered structure in which three transition metal oxygen layers and lithium oxygen layers are alternately arranged (i.e., a layered structure periodically arranged in the manner of transition metal oxygen layer 1-lithium oxygen layer 1-transition metal oxygen layer 2-lithium oxygen layer 2-transition metal oxygen layer 3-lithium oxygen layer 3).
- the lithium oxygen octahedron and the cobalt oxygen octahedron of the positive electrode material share an edge on one side and a plane on the other side; precisely because the lithium oxygen octahedron and the cobalt oxygen octahedron share the same plane in the positive electrode material, the repulsion between the cobalt oxygen layer and the lithium oxygen layer is greater, so the O-Li-O layer spacing will be larger, and the Li + diffusion channel will be smoother, so the rate performance of the positive electrode material will be better, and the structure of the positive electrode material enables it to obtain better electronic conductivity; the positive electrode material with this structural characteristic will undergo a series of phase changes during the charging and discharging process, and these phase changes enable the positive electrode material to release more Li + and obtain more capacity at the same voltage, so the capacity is higher than that of conventional lithium cobalt oxide; because these phase changes are reversible phase changes, they are completely reversible during the charging and discharging process, so
- the raw material for preparing the positive electrode material includes a sodium-containing compound, and the sodium-containing compound is selected from at least one of Na 2 CO 3 , NaOH and Na 2 C 2 O 4 .
- the molar ratio of Na in the sodium-containing compound to Co in the M1 metal-doped cobalt oxide precursor is 0.69-0.78:1.
- the raw materials for preparing the positive electrode material include a sodium-containing compound, a cobalt oxide precursor doped with an M1 metal, and an additive containing an M2 element.
- a sodium-containing precursor Na m Co 1-z1-z2 M 1 z1 M 2 z2 O 2 is further formed. Because the size of sodium ions is larger than that of lithium ions, the interlayer spacing in the sodium-containing precursor is larger. After sodium is replaced by lithium, the material can still maintain a relatively The large interlayer spacing can provide a larger channel for the migration of lithium ions, so that the obtained positive electrode material has a higher rate performance.
- C is the gram capacity of the positive electrode material, in mAh/g; x is the molar content of sodium in the positive electrode material; -50 ⁇ A ⁇ -100; 100 ⁇ B ⁇ 300, 0 ⁇ x ⁇ 0.1.
- 196 ⁇ C ⁇ 240 that is, the gram capacity of the positive electrode material is 196-240 mAh/g.
- the positive electrode material is obtained by replacing the sodium in the sodium-containing precursor with lithium, and exchange is a dynamic equilibrium process, which can be achieved by thermodynamically increasing the temperature or kinetically increasing the concentration difference, it is inevitable that there will be a certain amount of sodium residue.
- the positive electrode material When the sodium molar content x is 0.016, the positive electrode material has a discharge capacity of 202.37 mAh/g at 0.1C at a cut-off voltage of 4.5V, and a discharge capacity of 208.73 mAh/g at 0.5C at a cut-off voltage of 4.55V, which is much higher than the 186 mAh/g at 4.5V and 194 mAh/g at 4.55V of commercial lithium cobalt oxide.
- the present application also provides a method for preparing the above-mentioned positive electrode material, the method comprising the following steps:
- the cobalt oxide precursor doped with M1 metal is mixed with a sodium-containing compound in a ratio of Na to Co of 0.69 to 0.78:1, and the additive containing M2 element is mixed in a ratio of M2 to Co of 0.69 to 0.78:1.
- the molar ratio of the mixture is n2, 0 ⁇ n2 ⁇ 0.05;
- the soluble cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
- the soluble M1 salt is selected from at least one of nitrates, sulfates, oxalates and acetates containing the M1 element.
- the precipitant is, for example, 0.5-2 mol/L sodium hydroxide.
- the complexing agent is, for example, 0.5-2 mol/L ammonia water.
- step (1) after the sintering, the product is ground and sieved to obtain a cobalt tetroxide precursor doped with M1 metal, and the median particle size of the precursor is 3-20 ⁇ m.
- step (1) the precipitate is sintered at 600° C. to 900° C. for 10 h to 20 h in an air atmosphere.
- step (2) the mixture is sintered at 700° C. to 1000° C. for 24 h to 36 h in an oxygen atmosphere.
- the lithium salt is selected from at least one of lithium nitrate, lithium chloride, lithium bromide, lithium acetate, lithium carbonate or lithium hydroxide.
- the heating temperature is 100 to 300° C.
- the heating time is 0.5 to 8 hours
- the heating atmosphere is an air atmosphere.
- the present application also provides a positive electrode sheet, which includes the positive electrode material mentioned above.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one side or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent and a binder.
- the mass percentage of each component in the positive electrode active material layer is: 80-99.8wt% of positive electrode material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
- the mass percentage of each component in the positive electrode active material layer is: 90-99.6wt% of positive electrode material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
- the conductive agent is selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the binder is selected from at least one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), water-based acrylic resin, polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA) and polyvinyl alcohol (PVA).
- PVDF polyvinylidene fluoride
- CMC carboxymethyl cellulose
- SBR styrene-butadiene rubber
- water-based acrylic resin water-based acrylic resin
- PTFE polytetrafluoroethylene
- EVA ethylene-vinyl acetate copolymer
- PVA polyvinyl alcohol
- the positive electrode current collector is aluminum foil.
- the thickness of the positive electrode current collector is 6 to 10 ⁇ m.
- the thickness of the positive electrode active material layer is 60 to 100 ⁇ m.
- the compaction density of the positive electrode active material layer in the positive electrode sheet is 3.5 to 4.5 g/cm 3 .
- the present application also provides a battery, wherein the battery includes the above-mentioned positive electrode material, or the battery includes the above-mentioned positive electrode sheet.
- the battery can obtain reversible capacities of ⁇ 196 mAh/g and ⁇ 208 mAh/g at cut-off voltages of 3 to 4.5 V and 3 to 4.55 V, respectively.
- the present application provides a positive electrode material and a battery containing the positive electrode material.
- the positive electrode material has a high capacity, extremely high rate performance and good cycle performance.
- the full battery assembled with the positive electrode material can obtain a reversible capacity of ⁇ 196mAh/g and ⁇ 208mAh/g at a cut-off voltage of 3-4.5V and 3-4.55V, respectively, which is much higher than the currently commercially used LiCoO2 positive electrode material (only 186mAh/g at 3-4.5V, only 194mAh/g at 3-4.55V), and is expected to become a new type of alternative high-voltage material.
- FIG. 1 is a charge and discharge curve diagram of a battery composed of the positive electrode material of Example 1.
- FIG. 2 is a scanning electron microscope image of the positive electrode material of Example 1.
- Cobalt nitrate and aluminum sulfate were added to deionized water at a molar ratio of Co to Al of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.01 ) 3 O 4 ;
- Figure 1 is a charge and discharge curve diagram of a battery composed of the positive electrode material of Example 1.
- the positive electrode material when the sodium molar content x is 0.016, the positive electrode material has a discharge capacity of 202.37 mAh/g at a cut-off voltage of 4.5V at 0.1C, and the positive electrode material has a discharge capacity of 208.73 mAh/g at a cut-off voltage of 4.55V at 0.5C (not shown in the figure). It is much higher than the 186 mAh/g at 4.5V and 194 mAh/g at 4.55V of commercial lithium cobalt oxide (not shown in the figure). It shows that the positive electrode material has a higher capacity, and from its cycle performance and rate performance test results (Table 2), it can be seen that the positive electrode material has extremely high rate performance and good cycle performance.
- Figure 2 is a scanning electron microscope image of the positive electrode material of Example 1.
- the morphology of the positive electrode material is single crystal.
- Cobalt nitrate and nickel sulfate were added to deionized water at a molar ratio of Co to Ni of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Ni 0.01 ) 3 O 4 ;
- Cobalt nitrate and manganese sulfate were added to deionized water at a molar ratio of Co to Mn of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Mn 0.01 ) 3 O 4 ;
- Cobalt nitrate and magnesium sulfate were added to deionized water at a molar ratio of Co to Mg of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Mg 0.01 ) 3 O 4 ;
- Cobalt nitrate, aluminum sulfate and magnesium sulfate were added to deionized water at a molar ratio of Co:Al:Mg of 0.99:0.005:0.005, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900°C for 20 hours in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.005 Mg 0.005 ) 3 O 4 ;
- Cobalt nitrate and aluminum sulfate were added to deionized water at a molar ratio of Co to Al of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.01 ) 3 O 4 ;
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- Cobalt nitrate, aluminum sulfate and nickel nitrate were added to deionized water at a molar ratio of Co:Al:Ni of 0.99:0.005:0.005, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation.
- the precipitate was sintered at 900°C for 20 hours in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.005 Ni 0.005 ) 3 O 4 ;
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- Embodiment 19 is a diagrammatic representation of Embodiment 19:
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- LiCl and LiNO 3 LiCl and LiNO 3 mass ratio of 1:1
- Embodiment 23 is a diagrammatic representation of Embodiment 23.
- Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water in a molar ratio of 0.98:0.01:0.01, sodium carbonate and ammonia water are added as a precipitant and a complexing agent respectively, the pH is adjusted to 7-8 to precipitate, and the precipitant is sintered and ground to obtain (Co 0.98 Al 0.01 Mg 0.01 ) 3 O 4 ; then it is mixed with Li 2 CO 3 in a Li/Co molar ratio of 1.01:1, and sintered at 900°C in air for 12 hours to finally obtain LiCo 0.98 Al 0.01 Mg 0.01 O 2 , a traditional high-voltage lithium cobalt oxide material.
- Cobalt nitrate, aluminum sulfate, nickel nitrate and manganese sulfate were added to deionized water in a molar ratio of 0.97:0.01:0.01:0.01, sodium carbonate and ammonia water were added as a precipitant and a complexing agent respectively, and the pH was adjusted to 7-8 to precipitate, and the precipitant was sintered and ground to obtain (Co 0.97 Al 0.01 Ni 0.01 Mn 0.01 ) 3 O 4 ; then it was mixed with Li 2 CO 3 in a Li/Co molar ratio of 1.01:1, and sintered at 900°C in air for 12 hours to finally obtain Traditional high voltage lithium cobalt oxide material LiCo 0.97 Al 0.01 Ni 0.01 Mn 0.01 O 2 .
- Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to precipitate, the precipitant is sintered and ground to obtain a cobalt oxide compound doped with aluminum and magnesium; then it is mixed with Li2CO3 according to a Li/Co molar ratio of 1.01:1 and a Co:Al:Mg:Ti molar ratio of 0.97:0.01:0.01:0.01 and TiO2 , and then sintered at 900°C in air for 12 hours to finally obtain a traditional high-voltage lithium cobalt oxide material of LiCo 0.97 Al 0.01 Mg 0.01 Ti 0.01 O 2 .
- Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to precipitate, the precipitant is sintered and ground to obtain an aluminum-magnesium doped cobalt oxide precursor; then it is mixed with Li2CO3 at a Li/Co molar ratio of 1.01: 1 , and then mixed with TiO2 and ZrO2 to ensure that the molar ratio of Co:Al:Mg:Ti:Zr is 0.96: 0.01 : 0.01 : 0.01 , and sintered at 900°C in air for 12h to finally obtain LiCo0.96Al0.01Mg0.01Ti0.01Zr0.01O2 traditional high voltage lithium cobalt oxide material.
- Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to make it precipitate, and the precipitant is sintered and ground to obtain an aluminum-magnesium doped cobalt oxide precursor; then it is mixed with Li2CO3 at a Li/Co molar ratio of 1.01:1, and then mixed with TiO2 and Y2O3 to ensure that the ratio of Co:Al:Mg:Ti:Y is 0.96:0.01:0.01:0.01, and then sintered at 900°C in air for 12 hours to finally obtain LiCo 0.96 Al 0.01 Mg 0.01 Ti 0.01 Y 0.01 O 2 , a traditional high-voltage lithium cobalt oxide material.
- the positive electrode material, the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black are mixed according to the weight ratio 97:1.5:1.5, add N-methylpyrrolidone (NMP), and stir under the action of a vacuum stirrer until the mixed system becomes a positive electrode slurry with uniform fluidity; the positive electrode slurry is evenly coated on an aluminum foil with a thickness of 9 to 12 ⁇ m, and the compaction density is 4.0 g/cm 3 ; the coated aluminum foil is baked in an oven with 5 different temperature gradients, and then dried in an oven at 120° C. for 8 hours, and then rolled and cut to obtain the required positive electrode sheet.
- NMP N-methylpyrrolidone
- the positive electrode sheet, separator and negative electrode sheet prepared above are wound to obtain a bare battery cell without liquid injection; the bare battery cell is placed in an outer packaging foil, and the prepared electrolyte is injected into the dried bare battery cell. After vacuum packaging, standing, forming, shaping, sorting and other processes, the required lithium-ion battery is obtained.
- the molar content ratio m1 of the positive electrode materials of the test examples and comparative examples was measured; the positive electrode materials were then assembled into lithium-ion batteries, and the obtained lithium-ion battery finished product was discharged to 3.0V at a rate of 0.1C under the condition that the number of cycles N was less than 10, and the battery was disassembled after the battery was fully charged or half-charged (voltage>3.5V) was discharged to 3.0V, and the molar content ratio m2 of the positive electrode materials after discharge was measured.
- the test results are shown in Table 1.
- Table 1 Composition test results of positive electrode materials of Examples and Comparative Examples
- the positive electrode materials of the above embodiments and comparative examples, the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black were mixed in a weight ratio of 97:1.5:1.5, N-methylpyrrolidone (NMP) was added, and the mixture was stirred under the action of a vacuum stirrer until the mixture became a positive electrode slurry with uniform fluidity; the positive electrode slurry was evenly coated on an aluminum foil with a thickness of 9 to 12 ⁇ m, and the compaction density was 4.0 g/cm 3 ; the coated aluminum foil was baked in an oven with 5 different temperature gradients, and then dried in an oven at 120° C.
- NMP N-methylpyrrolidone
- the positive electrode sheet and the diaphragm were punched into diameters of 12 mm and 19 mm respectively using a button punching die, wherein the diaphragm was a 20 ⁇ m thick substrate diaphragm, the electrolyte was the electrolyte model mentioned in the above full battery, and the metal lithium negative electrode was assembled into a button battery (battery specification model was 2025).
- the charging rate is 0.1C, 0.5C, and 1C respectively.
- Discharge test and in the voltage range of 3 to 4.55V, charge and discharge cycles were performed at a rate of 0.5C for 100 cycles to test the 100T cycle capacity retention rate of the battery. The test results are shown in Table 2.
- the cathode material of the present application has a high capacity, extremely high rate performance, and good cycle performance.
- the extremely high rate performance means that it still has a high capacity at a high rate, which can be described by the ratio of the capacity at a high rate to the capacity at a low rate.
- the good cycle performance can be reflected by the ratio of the capacity after multiple cycles to the initial capacity, that is, the capacity retention rate.
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Abstract
A positive electrode material and a battery comprising same. The chemical formula of the positive electrode material is Lia-xNaxCo1-z1-z2M1
z1M2
z2O2, and the positive electrode material satisfies that: m1 is greater than m2, wherein m1 is the molar content ratio of Li/Na of the positive electrode material before charging and discharging, and m2 is the molar content ratio of Li/Na of the positive electrode material after discharging to 3.0 V according to the rate of 0.1 C. The positive electrode material has relatively high capacity, extremely high rate capability, and good cycle performance. A total battery assembled from the positive electrode material can obtain a reversible capacity greater than or equal to 196 mAh/g and a reversible capacity greater than or equal to 208 mAh/g respectively under cut-off voltages of 3-4.5 V and 3-4.55 V, and the reversible capacities are far higher than those that current commercially applied LiCoO2 positive electrode materials (only 186 mAh/g at 3-4.5 V and only 194 mAh/g at 3-4.55 V) can achieve. Thus, the positive electrode material is expected to become a novel alternative high-voltage material.
Description
本申请要求于2023年01月17日提交中国专利局、申请号为2023100579761、申请名称为“一种正极材料及包含该正极材料的电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the China Patent Office on January 17, 2023, with application number 2023100579761 and application name “A positive electrode material and a battery containing the positive electrode material”, the entire contents of which are incorporated by reference in this application.
本申请属于电池技术领域，具体涉及一种正极材料及包含该正极材料的电池。The present application belongs to the field of battery technology, and specifically relates to a positive electrode material and a battery containing the positive electrode material.
锂离子电池由于能量密度较高、循环性能好等优点，被广泛应用于各种便携式电子产品、交通工具以及储能设备等领域中。在3C领域，应用最广泛的是具有R-3m相结构的LiCoO2，因其具有较高的压实密度、较好的倍率性能和循环性能。目前为了满足日渐增长的高能量密度的需求，商业化的LiCoO2正朝着高电压(>4.5V vs.Li+/Li)方向发展。然而，当电压继续升高时，LiCoO2会发生严重的相变，如在4.55V附近的O3到H1-3相变，以及更高电压下的H1-3到O1相变，这种不可逆相变使得正极材料在高电压下的结构变得及其不稳定，晶体结构发生剧烈的c轴收缩，引起材料颗粒的破裂甚至破碎，从而导致循环失效。Lithium-ion batteries are widely used in various portable electronic products, transportation vehicles, energy storage devices and other fields due to their high energy density and good cycle performance. In the 3C field, the most widely used is LiCoO 2 with R-3m phase structure, because it has high compaction density, good rate performance and cycle performance. At present, in order to meet the growing demand for high energy density, commercial LiCoO 2 is developing towards high voltage (>4.5V vs.Li + /Li). However, when the voltage continues to increase, LiCoO 2 will undergo severe phase changes, such as the O3 to H1-3 phase change near 4.55V, and the H1-3 to O1 phase change at higher voltages. This irreversible phase change makes the structure of the positive electrode material extremely unstable at high voltages, and the crystal structure undergoes severe c-axis contraction, causing the material particles to rupture or even break, thereby leading to cycle failure.
为了抑制相变，研究者试图通过掺杂和包覆对其进行改善，但是掺杂和包覆量越多，往往会造成更多的容量损失，导致提容不提压的现象出现，并且高电压材料下对电解液也提出了更高的要求，高电压往往会导致电解液的氧化分解，副反应加剧；同时，电压过高还会造成材料表面的尖晶石相变，过渡金属溶出，从而导致电池的电化学性能急剧恶化。因此，目前迫切需要一种高容量、高倍率、在高电压下具有良好结构稳定性的正极材料。In order to suppress the phase change, researchers have tried to improve it by doping and coating. However, the more doping and coating, the more capacity loss will occur, resulting in the phenomenon of increasing capacity without increasing voltage. In addition, high voltage materials also place higher requirements on electrolytes. High voltage often leads to oxidative decomposition of electrolytes and aggravates side reactions. At the same time, excessive voltage will also cause spinel phase change on the surface of the material and dissolve transition metals, which will lead to a sharp deterioration in the electrochemical performance of the battery. Therefore, there is an urgent need for a positive electrode material with high capacity, high rate and good structural stability at high voltage.
发明内容
Summary of the invention
为了改善现有技术的不足，本申请的目的是提供一种正极材料及包含该正极材料的电池。所述正极材料在≤4.65V的充电截止电压下具有较高的容量、极高的倍率性能以及良好的循环性能，可以避免继续提升充电截止电压对电解液带来的氧化分解的风险，提高全电池的循环寿命。In order to improve the deficiencies of the prior art, the purpose of the present application is to provide a positive electrode material and a battery containing the positive electrode material. The positive electrode material has a high capacity, extremely high rate performance and good cycle performance at a charging cut-off voltage of ≤4.65V, which can avoid the risk of oxidative decomposition of the electrolyte caused by further increasing the charging cut-off voltage and improve the cycle life of the whole battery.
本申请目的是通过如下技术方案实现的：The purpose of this application is achieved through the following technical solutions:
一种正极材料，所述正极材料的化学式为Lia-xNaxCo1-z1-z2M1
z1M2
z2O2，其中0<x≤0.1，0.8≤a≤1，0≤z1≤0.07，0≤z2≤0.07，0.001≤z1+z2≤0.07，M1为Al、Mg、Mn、Ni中的至少一种，M2为Ti、Zr、B、P、Y、La、Te、Nb、W中的至少一种；A positive electrode material, the chemical formula of the positive electrode material is Li ax Na x Co 1-z1-z2 M 1 z1 M 2 z2 O 2 , wherein 0<x≤0.1, 0.8≤a≤1, 0≤z1≤0.07, 0≤z2≤0.07, 0.001≤z1+z2≤0.07, M1 is at least one of Al, Mg, Mn, and Ni, and M2 is at least one of Ti, Zr, B, P, Y, La, Te, Nb, and W;
所述正极材料满足：m1>m2；The positive electrode material satisfies: m1>m2;
其中，m1为所述正极材料在充放电前Li/Na的摩尔含量比；m2为所述正极材料按照0.1C倍率放电至3.0V后Li/Na的摩尔含量比。Wherein, m1 is the molar content ratio of Li/Na of the positive electrode material before charge and discharge; m2 is the molar content ratio of Li/Na after the positive electrode material is discharged to 3.0V at a rate of 0.1C.
根据本申请的实施方式，所述正极材料的Li/Na的摩尔含量比为a-x/x。According to an embodiment of the present application, the molar content ratio of Li/Na of the positive electrode material is a-x/x.
根据本申请的实施方式，m2为所述正极材料组装成锂离子电池后按照0.1C倍率放电至3.0V，拆解电池，测试放电后的正极材料的Li/Na的摩尔含量比。According to the implementation mode of the present application, m2 is the molar content ratio of Li/Na of the positive electrode material after being assembled into a lithium-ion battery and discharged to 3.0V at a rate of 0.1C, the battery is disassembled, and the discharged positive electrode material is tested.
根据本申请的实施方式，x为0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08或0.09。According to an embodiment of the present application, x is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08 or 0.09.
根据本申请的实施方式，a为0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98或0.99。According to an embodiment of the present application, a is 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99.
根据本申请的实施方式，z1+z2为0.002、0.003、0.004、0.005、0.006、0.007、0.008、0.009、0.01、0.02、0.03、0.04、0.05、0.06。According to an embodiment of the present application, z1+z2 is 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, or 0.06.
根据本申请的实施方式，所述正极材料中值粒径为3～20μm。所述正极材料选择这样的中值粒径可以避免锂离子迁移路径较长而导致增大电池内阻胀气的风险。According to the embodiment of the present application, the median particle size of the positive electrode material is 3-20 μm. The positive electrode material can avoid the risk of increasing the internal resistance and bloating of the battery due to a long lithium ion migration path by selecting such a median particle size.
根据本申请的实施方式，所述正极材料的比表面积为0.1～1.0m2/g。所述正极材料的比表面积过小时，会造成倍率性能不佳，而当正极材料的比表面积过大时，造成采用该正极材料的电池的电解液消耗增加。本申请的正极材料能够获得较好的倍率性能，且能避免电池在充放电过程中对电解液的过度消耗。
According to the embodiment of the present application, the specific surface area of the positive electrode material is 0.1 to 1.0 m 2 /g. If the specific surface area of the positive electrode material is too small, poor rate performance will result, while if the specific surface area of the positive electrode material is too large, increased electrolyte consumption of the battery using the positive electrode material will result. The positive electrode material of the present application can obtain better rate performance and can avoid excessive consumption of electrolyte during the charge and discharge process of the battery.
根据本申请的实施方式，所述正极材料的形貌为多晶或者单晶。According to an embodiment of the present application, the positive electrode material has a polycrystalline or single crystal morphology.
根据本申请的实施方式，所述正极材料的晶相结构为P63mc相结构。According to an embodiment of the present application, the crystal phase structure of the positive electrode material is a P63mc phase structure.
根据本申请的实施方式，所述正极材料具有较高的容量、极高的倍率性能，以及良好的循环性能。具体地，所述极高的倍率性能是指其在高倍率下仍具有较高的容量，可以通过高倍率下容量与低倍率下容量的比值来进行描述，循环性能好可以通过多次循环后的容量与初始容量的比值即容量保持率来体现。According to the embodiments of the present application, the positive electrode material has a high capacity, extremely high rate performance, and good cycle performance. Specifically, the extremely high rate performance means that it still has a high capacity at a high rate, which can be described by the ratio of the capacity at a high rate to the capacity at a low rate. Good cycle performance can be reflected by the ratio of the capacity after multiple cycles to the initial capacity, that is, the capacity retention rate.
根据本申请的实施方式，所述正极材料的每个重复单元中具有两层过渡金属氧层与锂氧层交替排布的层状结构(即按照过渡金属氧层1-锂氧层1-过渡金属氧层2-锂氧层2的方式进行周期性排布的层状结构)，且过渡金属原子和锂原子分别占据八面体位点。常规的钴酸锂的每个重复单元中具有三层过渡金属氧层与锂氧层交替排布的层状结构(即按照过渡金属氧层1-锂氧层1-过渡金属氧层2-锂氧层2-过渡金属氧层3-锂氧层3的方式进行周期性排布的层状结构)。According to the embodiment of the present application, each repeating unit of the positive electrode material has a layered structure in which two transition metal oxygen layers and lithium oxygen layers are alternately arranged (i.e., a layered structure periodically arranged in the manner of transition metal oxygen layer 1-lithium oxygen layer 1-transition metal oxygen layer 2-lithium oxygen layer 2), and the transition metal atoms and lithium atoms occupy octahedral sites respectively. Each repeating unit of conventional lithium cobalt oxide has a layered structure in which three transition metal oxygen layers and lithium oxygen layers are alternately arranged (i.e., a layered structure periodically arranged in the manner of transition metal oxygen layer 1-lithium oxygen layer 1-transition metal oxygen layer 2-lithium oxygen layer 2-transition metal oxygen layer 3-lithium oxygen layer 3).
根据本申请的实施方式，所述正极材料的锂氧八面体和钴氧八面体一侧共边，一侧共面；正是因为所述正极材料中存在锂氧八面体和钴氧八面体的共面，钴氧层与锂氧层之间的斥力更大，因此O-Li-O层间距会更大，Li+扩散的通道更顺畅，因此所述正极材料的倍率性能会更好，且所述正极材料的结构使其获得更好的电子导电性；该结构特性的正极材料在充放电过程中会发生一系列的相变，这些相变使得所述正极材料在相同电压下可以脱出更多的Li+获得更多容量，因此容量高于常规钴酸锂；因为这些相变均为可逆相变，在充电和放电过程中完全可逆，因此所述正极材料的循环性能优异。According to the implementation mode of the present application, the lithium oxygen octahedron and the cobalt oxygen octahedron of the positive electrode material share an edge on one side and a plane on the other side; precisely because the lithium oxygen octahedron and the cobalt oxygen octahedron share the same plane in the positive electrode material, the repulsion between the cobalt oxygen layer and the lithium oxygen layer is greater, so the O-Li-O layer spacing will be larger, and the Li + diffusion channel will be smoother, so the rate performance of the positive electrode material will be better, and the structure of the positive electrode material enables it to obtain better electronic conductivity; the positive electrode material with this structural characteristic will undergo a series of phase changes during the charging and discharging process, and these phase changes enable the positive electrode material to release more Li + and obtain more capacity at the same voltage, so the capacity is higher than that of conventional lithium cobalt oxide; because these phase changes are reversible phase changes, they are completely reversible during the charging and discharging process, so the positive electrode material has excellent cycle performance.
根据本申请的实施方式，所述正极材料的制备原料包括含钠化合物，所述含钠化合物选自Na2CO3、NaOH和Na2C2O4中的至少一种。According to an embodiment of the present application, the raw material for preparing the positive electrode material includes a sodium-containing compound, and the sodium-containing compound is selected from at least one of Na 2 CO 3 , NaOH and Na 2 C 2 O 4 .
根据本申请的实施方式，所述含钠化合物中的Na与含有M1金属掺杂的四氧化三钴前驱体中的Co的摩尔比为0.69～0.78:1。According to an embodiment of the present application, the molar ratio of Na in the sodium-containing compound to Co in the M1 metal-doped cobalt oxide precursor is 0.69-0.78:1.
根据本申请的实施方式，所述正极材料的制备原料包括含钠化合物和含有M1金属掺杂的四氧化三钴前驱体以及含有M2元素的添加剂，经过烧结后会进一步形成含钠的前驱体NamCo1-z1-z2M1
z1M2
z2O2，因为钠离子的尺寸较锂离子大，在含钠的前驱体中的层间距较大，钠被锂取代后，材料仍可以保持较
大的层间距，因此可以为锂离子的迁移提供更大的通道，从而获得的正极材料具有较高的倍率性能。According to the embodiment of the present application, the raw materials for preparing the positive electrode material include a sodium-containing compound, a cobalt oxide precursor doped with an M1 metal, and an additive containing an M2 element. After sintering, a sodium-containing precursor Na m Co 1-z1-z2 M 1 z1 M 2 z2 O 2 is further formed. Because the size of sodium ions is larger than that of lithium ions, the interlayer spacing in the sodium-containing precursor is larger. After sodium is replaced by lithium, the material can still maintain a relatively The large interlayer spacing can provide a larger channel for the migration of lithium ions, so that the obtained positive electrode material has a higher rate performance.
根据本申请的实施方式，所述正极材料满足如下关系式：
C＝Ax+B；According to an embodiment of the present application, the positive electrode material satisfies the following relationship:
C = Ax + B;
C＝Ax+B；According to an embodiment of the present application, the positive electrode material satisfies the following relationship:
C = Ax + B;
其中，C为正极材料的克容量，单位为mAh/g；x为正极材料中钠的摩尔含量；-50<A<-100；100<B<300，0<x≤0.1。Wherein, C is the gram capacity of the positive electrode material, in mAh/g; x is the molar content of sodium in the positive electrode material; -50<A<-100; 100<B<300, 0<x≤0.1.
根据本申请的实施方式，196≤C<240，即所述正极材料的克容量为196～240mAh/g。According to an embodiment of the present application, 196≤C<240, that is, the gram capacity of the positive electrode material is 196-240 mAh/g.
通过对不同截止电压下的正极材料进行克容量和钠摩尔含量的关系拟合，得到克容量与钠含量呈现一种负相关性，随着钠摩尔含量的增加，正极材料的克容量也在降低。这是因为在正极材料内部，钠会占据锂的位点，当钠摩尔含量增加时，相应的活性可脱嵌的Li+的数量就会减少，从而导致相应的容量的降低，同时Na的存在也在一定程度上阻碍了Li+的传输。由于所述正极材料是利用锂对含钠的前驱体中的钠进行替换而得到的，而交换是一种动态平衡的过程，可以通过热力学增加温度或者动力学增加浓度差来实现，因此不可避免会有一定的钠元素的残留。By fitting the relationship between the gram capacity and the molar content of sodium of the positive electrode material at different cut-off voltages, it is found that the gram capacity and the sodium content show a negative correlation. As the molar content of sodium increases, the gram capacity of the positive electrode material also decreases. This is because sodium will occupy the site of lithium inside the positive electrode material. When the molar content of sodium increases, the number of corresponding active and deintercalable Li + will decrease, resulting in a corresponding decrease in capacity. At the same time, the presence of Na also hinders the transmission of Li + to a certain extent. Since the positive electrode material is obtained by replacing the sodium in the sodium-containing precursor with lithium, and exchange is a dynamic equilibrium process, which can be achieved by thermodynamically increasing the temperature or kinetically increasing the concentration difference, it is inevitable that there will be a certain amount of sodium residue.
当钠摩尔含量x为0.016时，所述正极材料在4.5V的截止电压下，0.1C的放电容量可以达到202.37mAh/g，所述正极材料在4.55V的截止电压下，0.5C的放电容量可以达到208.73mAh/g。远高于商业化钴酸锂在4.5V时的186mAh/g和4.55V时的194mAh/g。When the sodium molar content x is 0.016, the positive electrode material has a discharge capacity of 202.37 mAh/g at 0.1C at a cut-off voltage of 4.5V, and a discharge capacity of 208.73 mAh/g at 0.5C at a cut-off voltage of 4.55V, which is much higher than the 186 mAh/g at 4.5V and 194 mAh/g at 4.55V of commercial lithium cobalt oxide.
本申请还提供上述正极材料的制备方法，所述方法包括如下步骤：The present application also provides a method for preparing the above-mentioned positive electrode material, the method comprising the following steps:
(1)将可溶性的Co盐和可溶性的M1盐按照M1与Co的摩尔比n1，0≤n1<0.05的比例加入到溶剂中，然后加入沉淀剂和络合剂，调节pH为6-10，使混合物形成共沉淀；将沉淀物进行烧结，获得含有M1金属掺杂的四氧化三钴前驱体；(1) adding a soluble Co salt and a soluble M1 salt into a solvent at a molar ratio of M1 to Co of n1, 0≤n1<0.05, then adding a precipitant and a complexing agent, adjusting the pH to 6-10, so that the mixture forms a coprecipitation; sintering the precipitate to obtain a cobalt oxide precursor doped with M1 metal;
(2)将含有M1金属掺杂的四氧化三钴前驱体与含钠化合物和含有M2元素的添加剂进行混合，对混合物进行烧结，获得NamCo1-z1-z2M1
z1M2
z2O2，0.65≤m<1，0.001≤z1+z2≤0.07；(2) mixing a cobalt oxide precursor doped with an M1 metal with a sodium compound and an additive containing an M2 element, and sintering the mixture to obtain NamCo1 -z1-z2M1z1M2z2O2 , 0.65≤m < 1 , 0.001≤z1 + z2≤0.07 ;
其中，将含有M1金属掺杂的四氧化三钴前驱体与含钠化合物按照Na与Co的摩尔比为0.69～0.78:1的比例混合，含有M2元素的添加剂按照M2与Co
的摩尔比为n2的比例混合，0≤n2<0.05；The cobalt oxide precursor doped with M1 metal is mixed with a sodium-containing compound in a ratio of Na to Co of 0.69 to 0.78:1, and the additive containing M2 element is mixed in a ratio of M2 to Co of 0.69 to 0.78:1. The molar ratio of the mixture is n2, 0≤n2<0.05;
(3)将NamCo1-z1-z2M1
z1M2
z2O2与锂盐按照Li与Na的摩尔比为5～10:1的比例混合，加热，制备得到所述正极材料。(3) Na m Co 1-z1-z2 M 1 z1 M 2 z2 O 2 and lithium salt are mixed in a molar ratio of Li to Na of 5 to 10:1, and heated to prepare the positive electrode material.
根据本申请的实施方式，步骤(1)中，所述可溶性的钴盐选自氯化钴、硫酸钴、硝酸钴和醋酸钴中的至少一种。According to an embodiment of the present application, in step (1), the soluble cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
根据本申请的实施方式，步骤(1)中，所述可溶性的M1盐选自含有M1元素的硝酸盐、硫酸盐、草酸盐和醋酸盐中的至少一种。According to an embodiment of the present application, in step (1), the soluble M1 salt is selected from at least one of nitrates, sulfates, oxalates and acetates containing the M1 element.
根据本申请的实施方式，步骤(1)中，所述沉淀剂例如为0.5-2mol/L的氢氧化钠。According to an embodiment of the present application, in step (1), the precipitant is, for example, 0.5-2 mol/L sodium hydroxide.
根据本申请的实施方式，步骤(1)中，所述络合剂例如为0.5-2mol/L的氨水。According to an embodiment of the present application, in step (1), the complexing agent is, for example, 0.5-2 mol/L ammonia water.
根据本申请的实施方式，步骤(1)中，所述烧结后，对产物进行研磨过筛处理，从而获得含有M1金属掺杂的四氧化三钴前驱体，前驱体的中值粒径为3-20μm。According to an embodiment of the present application, in step (1), after the sintering, the product is ground and sieved to obtain a cobalt tetroxide precursor doped with M1 metal, and the median particle size of the precursor is 3-20 μm.
根据本申请的实施方式，步骤(1)中，将沉淀物在空气氛围下在600℃～900℃下烧结10h～20h。According to an embodiment of the present application, in step (1), the precipitate is sintered at 600° C. to 900° C. for 10 h to 20 h in an air atmosphere.
根据本申请的实施方式，步骤(2)中，将混合物在氧气氛围下在700℃～1000℃下烧结24h～36h。According to an embodiment of the present application, in step (2), the mixture is sintered at 700° C. to 1000° C. for 24 h to 36 h in an oxygen atmosphere.
根据本申请的实施方式，步骤(3)中，所述锂盐选自硝酸锂、氯化锂、溴化锂、醋酸锂、碳酸锂或者氢氧化锂中的至少一种。According to an embodiment of the present application, in step (3), the lithium salt is selected from at least one of lithium nitrate, lithium chloride, lithium bromide, lithium acetate, lithium carbonate or lithium hydroxide.
根据本申请的实施方式，步骤(3)中，所述加热的温度为100～300℃，所述加热的时间为0.5～8小时，所述加热的气氛为空气气氛。According to an embodiment of the present application, in step (3), the heating temperature is 100 to 300° C., the heating time is 0.5 to 8 hours, and the heating atmosphere is an air atmosphere.
本申请还提供一种正极片，所述正极片包括上述的正极材料。The present application also provides a positive electrode sheet, which includes the positive electrode material mentioned above.
根据本申请的实施方式，所述正极片包括正极集流体和涂覆在正极集流体一侧或两侧表面的正极活性物质层，所述正极活性物质层包括正极活性物质、导电剂和粘结剂。According to an embodiment of the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one side or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent and a binder.
根据本申请的实施方式，所述正极活性物质层中各组分的质量百分含量为：80～99.8wt％的正极材料、0.1～10wt％的导电剂、0.1～10wt％的粘结剂。According to an embodiment of the present application, the mass percentage of each component in the positive electrode active material layer is: 80-99.8wt% of positive electrode material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
优选地，所述正极活性物质层中各组分的质量百分含量为：90～99.6wt％的正极材料、0.2～5wt％的导电剂、0.2～5wt％的粘结剂。
Preferably, the mass percentage of each component in the positive electrode active material layer is: 90-99.6wt% of positive electrode material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
根据本申请的实施方式，所述导电剂选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。According to an embodiment of the present application, the conductive agent is selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
根据本申请的实施方式，所述粘结剂选自聚偏二氟乙烯(PVDF)、羧甲基纤维素(CMC)、丁苯橡胶(SBR)、水性丙烯酸树脂、聚四氟乙烯(PTFE)、乙烯-醋酸乙烯酯共聚物(EVA)及聚乙烯醇(PVA)中的至少一种。According to an embodiment of the present application, the binder is selected from at least one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), water-based acrylic resin, polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA) and polyvinyl alcohol (PVA).
根据本申请的实施方式，所述正极集流体为铝箔。According to an embodiment of the present application, the positive electrode current collector is aluminum foil.
根据本申请的实施方式，所述正极集流体的厚度为6～10μm。According to an embodiment of the present application, the thickness of the positive electrode current collector is 6 to 10 μm.
根据本申请的实施方式，所述正极活性物质层的厚度为60～100μm。According to an embodiment of the present application, the thickness of the positive electrode active material layer is 60 to 100 μm.
根据本申请的实施方式，所述正极片中正极活性物质层的压实密度为3.5～4.5g/cm3。According to an embodiment of the present application, the compaction density of the positive electrode active material layer in the positive electrode sheet is 3.5 to 4.5 g/cm 3 .
本申请还提供一种电池，所述电池包括上述的正极材料，或者所述电池包括上述的正极片。The present application also provides a battery, wherein the battery includes the above-mentioned positive electrode material, or the battery includes the above-mentioned positive electrode sheet.
根据本申请的实施方式，所述电池在3～4.5V和3～4.55V的截止电压下分别可以获得≥196mAh/g和≥208mAh/g的可逆容量。According to the embodiments of the present application, the battery can obtain reversible capacities of ≥196 mAh/g and ≥208 mAh/g at cut-off voltages of 3 to 4.5 V and 3 to 4.55 V, respectively.
本申请的有益效果：Beneficial effects of this application:
本申请提供了一种正极材料及包含该正极材料的电池。所述正极材料具有较高的容量、极高的倍率性能以及良好的循环性能。所述正极材料组装的全电池在3～4.5V和3～4.55V的截止电压下分别可以获得≥196mAh/g和≥208mAh/g的可逆容量，远高于目前商业化应用的LiCoO2正极材料(3～4.5V仅186mAh/g，3～4.55V仅194mAh/g)，有望成为一种新型替代型高电压材料。The present application provides a positive electrode material and a battery containing the positive electrode material. The positive electrode material has a high capacity, extremely high rate performance and good cycle performance. The full battery assembled with the positive electrode material can obtain a reversible capacity of ≥196mAh/g and ≥208mAh/g at a cut-off voltage of 3-4.5V and 3-4.55V, respectively, which is much higher than the currently commercially used LiCoO2 positive electrode material (only 186mAh/g at 3-4.5V, only 194mAh/g at 3-4.55V), and is expected to become a new type of alternative high-voltage material.
图1为实施例1的正极材料组成的电池的充放电曲线图。FIG. 1 is a charge and discharge curve diagram of a battery composed of the positive electrode material of Example 1.
图2为实施例1的正极材料的扫描电镜图。FIG. 2 is a scanning electron microscope image of the positive electrode material of Example 1.
下文将结合具体实施例对本申请做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。
The present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary illustrations and explanations of the present application and should not be construed as limiting the scope of protection of the present application. All technologies implemented based on the above content of the present application are included in the scope that the present application is intended to protect.
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.
实施例1Example 1
(1)将硝酸钴和硫酸铝按照Co与Al的摩尔比为0.99:0.01的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Al0.01)3O4；(1) Cobalt nitrate and aluminum sulfate were added to deionized water at a molar ratio of Co to Al of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.01 ) 3 O 4 ;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.70:0.99的比例均匀混合，通氧气在950℃下烧结36h，获得Na0.70Co0.99Al0.01O2；(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.70:0.99, and sintered at 950°C for 36 h in an atmosphere of oxygen to obtain Na 0.70 Co 0.99 Al 0.01 O 2 ;
(3)将Na0.70Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为10，最终获得Li0.98Na0.016Co0.99Al0.01O2。(3) Na 0.70 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 10, and finally Li 0.98 Na 0.016 Co 0.99 Al 0.01 O 2 was obtained.
图1为实施例1的正极材料组成的电池的充放电曲线图。从图1中可以看出，当钠摩尔含量x为0.016时，所述正极材料在4.5V的截止电压下，0.1C的放电容量可以达到202.37mAh/g，所述正极材料在4.55V的截止电压下，0.5C的放电容量可以达到208.73mAh/g(图中未示出)。远高于商业化钴酸锂在4.5V时的186mAh/g和4.55V时的194mAh/g(图中未示出)。说明所述正极材料具有较高的容量，且从其循环性能和倍率性能测试结果(表2)可以看出，所述正极材料具有极高的倍率性能以及良好的循环性能。Figure 1 is a charge and discharge curve diagram of a battery composed of the positive electrode material of Example 1. As can be seen from Figure 1, when the sodium molar content x is 0.016, the positive electrode material has a discharge capacity of 202.37 mAh/g at a cut-off voltage of 4.5V at 0.1C, and the positive electrode material has a discharge capacity of 208.73 mAh/g at a cut-off voltage of 4.55V at 0.5C (not shown in the figure). It is much higher than the 186 mAh/g at 4.5V and 194 mAh/g at 4.55V of commercial lithium cobalt oxide (not shown in the figure). It shows that the positive electrode material has a higher capacity, and from its cycle performance and rate performance test results (Table 2), it can be seen that the positive electrode material has extremely high rate performance and good cycle performance.
图2为实施例1的正极材料的扫描电镜图。所述正极材料的形貌为单晶。Figure 2 is a scanning electron microscope image of the positive electrode material of Example 1. The morphology of the positive electrode material is single crystal.
实施例2Example 2
(1)将硝酸钴和硫酸镍按照Co与Ni的摩尔比为0.99:0.01的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Ni0.01)3O4；(1) Cobalt nitrate and nickel sulfate were added to deionized water at a molar ratio of Co to Ni of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Ni 0.01 ) 3 O 4 ;
(2)将(Co0.99Ni0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.70:0.99
的比例均匀混合，通氧气在950℃下烧结36h，获得Na0.70Co0.99Ni0.01O2；(2) (Co 0.99 Ni 0.01 ) 3 O 4 and Na 2 CO 3 were mixed in a Na to Co molar ratio of 0.70:0.99. The mixture was uniformly mixed in a ratio of , and sintered at 950°C for 36 hours with oxygen passing therethrough to obtain Na 0.70 Co 0.99 Ni 0.01 O 2 ;
(3)将Na0.70Co0.99Ni0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为10，最终获得Li0.97Na0.021Co0.99Ni0.01O2。(3) Na 0.70 Co 0.99 Ni 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 10, and finally Li 0.97 Na 0.021 Co 0.99 Ni 0.01 O 2 was obtained.
实施例3Example 3
(1)将硝酸钴和硫酸锰按照Co与Mn的摩尔比为0.99:0.01的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Mn0.01)3O4；(1) Cobalt nitrate and manganese sulfate were added to deionized water at a molar ratio of Co to Mn of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Mn 0.01 ) 3 O 4 ;
(2)将(Co0.99Mn0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.70:0.99的比例均匀混合，通氧气在950℃下烧结36h，获得Na0.70Co0.99Mn0.01O2；(2) (Co 0.99 Mn 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.70:0.99, and sintered at 950°C for 36 h in the presence of oxygen to obtain Na 0.70 Co 0.99 Mn 0.01 O 2 ;
(3)将Na0.70Co0.99Mn0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为10，最终获得Li0.97Na0.024Co0.99Mn0.01O2。(3) Na 0.70 Co 0.99 Mn 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 10, and finally Li 0.97 Na 0.024 Co 0.99 Mn 0.01 O 2 was obtained.
实施例4Example 4
(1)同实施例1；(1) Same as Example 1;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.72:0.99的比例均匀混合，通氧气在900℃下烧结36h，获得Na0.72Co0.99Al0.01O2；(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.72:0.99, and sintered at 900°C for 36 h in an atmosphere of oxygen to obtain Na 0.72 Co 0.99 Al 0.01 O 2 ;
(3)将Na0.72Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为9，最终获得Li0.97Na0.025Co0.99Al0.01O2。(3) Na 0.72 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 9, and finally Li 0.97 Na 0.025 Co 0.99 Al 0.01 O 2 was obtained.
实施例5Example 5
(1)同实施例3；(1) Same as Example 3;
(2)将(Co0.99Mn0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.72:0.99的比例均匀混合，通氧气在900℃下烧结36h，获得Na0.72Co0.99Mn0.01O2；(2) (Co 0.99 Mn 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.72:0.99, and sintered at 900°C for 36 h in an atmosphere of oxygen to obtain Na 0.72 Co 0.99 Mn 0.01 O 2 ;
(3)将Na0.72Co0.99Mn0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为9，最终获得
Li0.96Na0.034Co0.99Mn0.01O2。(3) Na 0.72 Co 0.99 Mn 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio 1:1) and heated to melt at 300 °C to ensure that the Li/Na molar ratio was 9, and finally obtained Li 0.96 Na 0.034 Co 0.99 Mn 0.01 O 2 .
实施例6Example 6
(1)将硝酸钴和硫酸镁按照Co与Mg的摩尔比为0.99:0.01的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Mg0.01)3O4；(1) Cobalt nitrate and magnesium sulfate were added to deionized water at a molar ratio of Co to Mg of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Mg 0.01 ) 3 O 4 ;
(2)将(Co0.99Mg0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.72:0.99的比例均匀混合，通氧气在900℃下烧结36h，获得Na0.72Co0.99Mg0.01O2；(2) (Co 0.99 Mg 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.72:0.99, and sintered at 900°C for 36 h in an atmosphere of oxygen to obtain Na 0.72 Co 0.99 Mg 0.01 O 2 ;
(3)将Na0.72Co0.99Mg0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为9，最终获得Li0.96Na0.035Co0.99Mg0.01O2。(3) Na 0.72 Co 0.99 Mg 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 9, and finally Li 0.96 Na 0.035 Co 0.99 Mg 0.01 O 2 was obtained.
实施例7Example 7
(1)将硝酸钴加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得Co3O4；(1) Add cobalt nitrate to deionized water, then add 0.05 mol/L sodium hydroxide and ammonia water, adjust the pH to 6-8, and form a precipitate in the mixture. Sinter the precipitate at 900°C for 20 hours in an air atmosphere, and grind and sieve the product to obtain Co 3 O 4 ;
(2)将Co3O4、Na2CO3和TiO2按照Na：Co：Ti的摩尔比为0.72:0.99:0.01的比例均匀混合，通氧气在900℃下烧结36h，获得Na0.72Co0.99Ti0.01O2；(2) Co 3 O 4 , Na 2 CO 3 and TiO 2 were uniformly mixed in a molar ratio of Na:Co:Ti of 0.72:0.99:0.01, and sintered at 900°C for 36 h in an atmosphere of oxygen to obtain Na 0.72 Co 0.99 Ti 0.01 O 2 ;
(3)将Na0.72Co0.99Ti0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为9，最终获得Li0.96Na0.035Co0.99Ti0.01O2。(3) Na 0.72 Co 0.99 Ti 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 9, and finally Li 0.96 Na 0.035 Co 0.99 Ti 0.01 O 2 was obtained.
实施例8Example 8
(1)同实施例2；(1) Same as Example 2;
(2)将(Co0.99Ni0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.72:0.99的比例均匀混合，通氧气在900℃下烧结36h，获得Na0.72Co0.99Ni0.01O2；(2) (Co 0.99 Ni 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.72:0.99, and sintered at 900°C for 36 h in an atmosphere of oxygen to obtain Na 0.72 Co 0.99 Ni 0.01 O 2 ;
(3)将Na0.72Co0.99Ni0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为9，最终获得
Li0.96Na0.036Co0.99Ni0.01O2。(3) Na 0.72 Co 0.99 Ni 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio 1:1) and heated to melt at 300 °C to ensure that the Li/Na molar ratio was 9, and finally obtained Li 0.96 Na 0.036 Co 0.99 Ni 0.01 O 2 .
实施例9Example 9
(1)同实施例1；(1) Same as Example 1;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.74:0.99的比例均匀混合，通氧气在850℃下烧结36h，获得Na0.74Co0.99Al0.01O2；(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.74:0.99, and sintered at 850°C for 36 h in an atmosphere of oxygen to obtain Na 0.74 Co 0.99 Al 0.01 O 2 ;
(3)将Na0.74Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为8，最终获得Li0.96Na0.037Co0.99Al0.01O2。(3) Na 0.74 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 8, and finally Li 0.96 Na 0.037 Co 0.99 Al 0.01 O 2 was obtained.
实施例10Example 10
(1)将硝酸钴和硫酸铝和硫酸镁按照Co:Al:Mg的摩尔比为0.99:0.005:0.005的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Al0.005Mg0.005)3O4；(1) Cobalt nitrate, aluminum sulfate and magnesium sulfate were added to deionized water at a molar ratio of Co:Al:Mg of 0.99:0.005:0.005, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900°C for 20 hours in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.005 Mg 0.005 ) 3 O 4 ;
(2)将(Co0.99Al0.005Mg0.005)3O4与Na2CO3按照Na与Co的摩尔比为0.74:0.99的比例均匀混合，通氧气在850℃下烧结36h，获得Na0.74Co0.99Al0.005Mg0.005O2；(2) (Co 0.99 Al 0.005 Mg 0.005 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.74:0.99, and sintered at 850°C for 36 h in the presence of oxygen to obtain Na 0.74 Co 0.99 Al 0.005 Mg 0.005 O 2 ;
(3)将Na0.74Co0.99Al0.005Mg0.005O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为8，最终获得Li0.96Na0.037Co0.99Al0.005Mg0.005O2。(3) Na 0.74 Co 0.99 Al 0.005 Mg 0.005 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl and LiNO 3 was 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 8, and finally Li 0.96 Na 0.037 Co 0.99 Al 0.005 Mg 0.005 O 2 was obtained.
实施例11Embodiment 11
(1)将硝酸钴和硫酸铝按照Co与Al的摩尔比为0.99:0.01的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Al0.01)3O4；(1) Cobalt nitrate and aluminum sulfate were added to deionized water at a molar ratio of Co to Al of 0.99:0.01, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900° C. for 20 h in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.01 ) 3 O 4 ;
(2)将(Co0.99Al0.01)3O4与Na2CO3以及TiO2进行混合，保证Na：Co：Al：Ti的摩尔比为0.74:0.99：0.005：0.005的比例均匀混合，通氧气在850℃
下烧结36h，获得Na0.74Co0.99Al0.005Ti0.005O2；(2) Mix (Co 0.99 Al 0.01 ) 3 O 4 with Na 2 CO 3 and TiO 2 to ensure that the molar ratio of Na:Co:Al:Ti is 0.74:0.99:0.005:0.005 and mix them evenly. Pass oxygen at 850°C. Sintered at 37°C for 36 h to obtain Na 0.74 Co 0.99 Al 0.005 Ti 0.005 O 2 ;
(3)将Na0.74Co0.99Al0.005Ti0.005O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na为8，最终获得Li0.96Na0.039Co0.99Al0.005Ti0.005O2。(3) Na 0.74 Co 0.99 Al 0.005 Ti 0.005 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio of 1:1) and heated to melt at 300°C to ensure that the Li/Na ratio was 8, and finally Li 0.96 Na 0.039 Co 0.99 Al 0.005 Ti 0.005 O 2 was obtained.
实施例12Example 12
(1)同实施例11；(1) Same as Example 11;
(2)将(Co0.99Al0.01)3O4与Na2CO3以及ZrO2进行混合，保证按照Na：Co：Al：Zr的摩尔比为0.74:0.99：0.005：0.005的比例均匀混合，通氧气在850℃下烧结36h，获得Na0.74Co0.99Al0.005Zr0.005O2；(2) mixing (Co 0.99 Al 0.01 ) 3 O 4 with Na 2 CO 3 and ZrO 2 to ensure that the mixture is uniformly mixed in a molar ratio of Na:Co:Al:Zr of 0.74:0.99:0.005:0.005, and sintering at 850°C for 36 hours in an atmosphere of oxygen to obtain Na 0.74 Co 0.99 Al 0.005 Zr 0.005 O 2 ;
(3)将Na0.74Co0.99Al0.005Zr0.005O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为8，最终获得Li0.96Na0.039Co0.99Al0.005Zr0.005O2。(3) Na 0.74 Co 0.99 Al 0.005 Zr 0.005 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl and LiNO 3 was 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 8, and finally Li 0.96 Na 0.039 Co 0.99 Al 0.005 Zr 0.005 O 2 was obtained.
实施例13Example 13
(1)将硝酸钴、硫酸铝和硝酸镍按照Co：Al：Ni的摩尔比为0.99:0.005:0.005的比例加入到去离子水中，然后加入0.05mol/L的氢氧化钠和氨水，调节pH为6-8，使混合物形成共沉淀。将沉淀物在空气氛围下在900℃下烧结20h后，对产物进行研磨过筛处理，从而获得(Co0.99Al0.005Ni0.005)3O4；(1) Cobalt nitrate, aluminum sulfate and nickel nitrate were added to deionized water at a molar ratio of Co:Al:Ni of 0.99:0.005:0.005, and then 0.05 mol/L sodium hydroxide and ammonia water were added to adjust the pH to 6-8, so that the mixture formed a coprecipitation. The precipitate was sintered at 900°C for 20 hours in an air atmosphere, and the product was ground and sieved to obtain (Co 0.99 Al 0.005 Ni 0.005 ) 3 O 4 ;
(2)将(Co0.99Al0.005Ni0.005)3O4与Na2CO3按照Na与Co的摩尔比为0.74:0.99的比例均匀混合，通氧气在850℃下烧结36h，获得Na0.74Co0.99Al0.005Ni0.005O2；(2) (Co 0.99 Al 0.005 Ni 0.005 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.74:0.99, and sintered at 850°C for 36 h in the presence of oxygen to obtain Na 0.74 Co 0.99 Al 0.005 Ni 0.005 O 2 ;
(3)将Na0.74Co0.99Al0.005Ni0.005O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为8，最终获得Li0.95Na0.042Co0.99Al0.005Ni0.005O2。(3) Na 0.74 Co 0.99 Al 0.005 Ni 0.005 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl and LiNO 3 was 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 8, and finally Li 0.95 Na 0.042 Co 0.99 Al 0.005 Ni 0.005 O 2 was obtained.
实施例14Embodiment 14
(1)同实施例1；(1) Same as Example 1;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99
的比例均匀混合，通氧气在800℃下烧结36h，获得Na0.76Co0.99Al0.01O2；(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were mixed in a Na to Co molar ratio of 0.76:0.99. The mixture was uniformly mixed in a ratio of , and sintered at 800°C for 36 hours with oxygen passing therethrough to obtain Na 0.76 Co 0.99 Al 0.01 O 2 ;
(3)将Na0.76Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为7，最终获得Li0.95Na0.045Co0.99Al0.01O2。(3) Na 0.76 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio of 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 7, and finally Li 0.95 Na 0.045 Co 0.99 Al 0.01 O 2 was obtained.
实施例15Embodiment 15
(1)同实施例14；(1) Same as Example 14;
(2)同实施例14；(2) Same as Example 14;
(3)将Na0.76Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.94Na0.055Co0.99Al0.01O2。(3) Na 0.76 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio of 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.94 Na 0.055 Co 0.99 Al 0.01 O 2 was obtained.
实施例16Example 16
(1)同实施例6；(1) Same as Example 6;
(2)将(Co0.99Mg0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在800℃下烧结36h，获得Na0.76Co0.99Mg0.01O2；(2) (Co 0.99 Mg 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 800°C for 36 h in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Mg 0.01 O 2 ;
(3)将Na0.76Co0.99Mg0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)后在300℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.94Na0.059Co0.99Mg0.01O2。(3) Na 0.76 Co 0.99 Mg 0.01 O 2 was heated and melted with LiCl and LiNO 3 (the mass ratio of LiCl and LiNO 3 was 1:1) at 300°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.94 Na 0.059 Co 0.99 Mg 0.01 O 2 was obtained.
实施例17Embodiment 17
(1)同实施例2；(1) Same as Example 2;
(2)将(Co0.99Ni0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在800℃下烧结36h，获得Na0.76Co0.99Ni0.01O2；(2) (Co 0.99 Ni 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 800°C for 36 hours in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Ni 0.01 O 2 ;
(3)将Na0.76Co0.99Ni0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.93Na0.061Co0.99Ni0.01O2。(3) Na 0.76 Co 0.99 Ni 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 300°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.93 Na 0.061 Co 0.99 Ni 0.01 O 2 was obtained.
实施例18Embodiment 18
(1)同实施例3；
(1) Same as Example 3;
(2)将(Co0.99Mn0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在800℃下烧结36h，获得Na0.76Co0.99Mn0.01O2；(2) (Co 0.99 Mn 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 800°C for 36 h in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Mn 0.01 O 2 ;
(3)将Na0.76Co0.99Mn0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在300℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.93Na0.063Co0.99Mn0.01O2。(3) Na 0.76 Co 0.99 Mn 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and heated to melt at 300°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.93 Na 0.063 Co 0.99 Mn 0.01 O 2 was obtained.
实施例19：Embodiment 19:
(1)同实施例1；(1) Same as Example 1;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在750℃下烧结36h,获得Na0.76Co0.99Al0.01O2；(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 750°C for 36 hours in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Al 0.01 O 2 ;
(3)将Na0.76Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在250℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.93Na0.065Co0.99Al0.01O2。(3) Na 0.76 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 250°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.93 Na 0.065 Co 0.99 Al 0.01 O 2 was obtained.
实施例20Embodiment 20
(1)同实施例6；(1) Same as Example 6;
(2)将(Co0.99Mg0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在750℃下烧结36h，获得Na0.76Co0.99Mg0.01O2；(2) (Co 0.99 Mg 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 750°C for 36 h in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Mg 0.01 O 2 ;
(3)将Na0.76Co0.99Mg0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在250℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.93Na0.069Co0.99Mg0.01O2。(3) Na 0.76 Co 0.99 Mg 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio of 1:1) and heated to melt at 250°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.93 Na 0.069 Co 0.99 Mg 0.01 O 2 was obtained.
实施例21Embodiment 21
(1)同实施例2；(1) Same as Example 2;
(2)将(Co0.99Ni0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在750℃下烧结36h,获得Na0.76Co0.99Ni0.01O2；(2) (Co 0.99 Ni 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 750°C for 36 hours in an atmosphere of oxygen to obtain Na 0.76 Co 0.99 Ni 0.01 O 2 ;
(3)将Na0.76Co0.99Ni0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在250℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.92Na0.071Co0.99Ni0.01O2。
(3) Na 0.76 Co 0.99 Ni 0.01 O 2 was mixed with LiCl and LiNO 3 (LiCl and LiNO 3 mass ratio of 1:1) and heated to melt at 250°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.92 Na 0.071 Co 0.99 Ni 0.01 O 2 was obtained.
实施例22Embodiment 22
(1)同实施例7；(1) Same as Example 7;
(2)将Co3O4、Na2CO3和TiO2按照Na：Co：Ti的摩尔比为0.76:0.99:0.01的比例均匀混合，通氧气在750℃下烧结36h，获得Na0.76Co0.99Ti0.01O2；(2) Co 3 O 4 , Na 2 CO 3 and TiO 2 were uniformly mixed in a molar ratio of Na:Co:Ti of 0.76:0.99:0.01, and sintered at 750°C for 36 h in the presence of oxygen to obtain Na 0.76 Co 0.99 Ti 0.01 O 2 ;
(3)将Na0.76Co0.99Ti0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在250℃下加热熔融，保证Li/Na摩尔比为6，最终获得Li0.92Na0.073Co0.99Ti0.01O2。(3) Na 0.76 Co 0.99 Ti 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 250°C to ensure that the Li/Na molar ratio was 6, and finally Li 0.92 Na 0.073 Co 0.99 Ti 0.01 O 2 was obtained.
实施例23：Embodiment 23:
(1)同实施例1；(1) Same as Example 1;
(2)将(Co0.99Al0.01)3O4与Na2CO3按照Na与Co的摩尔比为0.76:0.99的比例均匀混合，通氧气在700℃下烧结36h,获得Na0.76Co0.99Al0.01O2。(2) (Co 0.99 Al 0.01 ) 3 O 4 and Na 2 CO 3 were uniformly mixed in a molar ratio of Na to Co of 0.76:0.99, and sintered at 700°C for 36 hours in the presence of oxygen to obtain Na 0.76 Co 0.99 Al 0.01 O 2 .
(3)将Na0.76Co0.99Al0.01O2与LiCl和LiNO3(LiCl和LiNO3质量比1:1)混合后在200℃下加热熔融，保证Li/Na摩尔比为5，最终获得Li0.92Na0.075Co0.99Al0.01O2。(3) Na 0.76 Co 0.99 Al 0.01 O 2 was mixed with LiCl and LiNO 3 (the mass ratio of LiCl to LiNO 3 was 1:1) and then heated to melt at 200°C to ensure that the Li/Na molar ratio was 5, and finally Li 0.92 Na 0.075 Co 0.99 Al 0.01 O 2 was obtained.
对比例1：Comparative Example 1:
将硝酸钴、硫酸铝和硫酸镁按照摩尔比为0.98:0.01:0.01的比例加入到去离子水中，加入碳酸钠和氨水分别作为沉淀剂和络合剂，调节pH为7～8，使其沉淀，对沉淀剂进行烧结和研磨获得(Co0.98Al0.01Mg0.01)3O4；然后将其与Li2CO3按照Li/Co摩尔比为1.01:1的比例进行混合后，在空气中900℃烧结12h，最终获得LiCo0.98Al0.01Mg0.01O2的传统高电压钴酸锂材料。Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water in a molar ratio of 0.98:0.01:0.01, sodium carbonate and ammonia water are added as a precipitant and a complexing agent respectively, the pH is adjusted to 7-8 to precipitate, and the precipitant is sintered and ground to obtain (Co 0.98 Al 0.01 Mg 0.01 ) 3 O 4 ; then it is mixed with Li 2 CO 3 in a Li/Co molar ratio of 1.01:1, and sintered at 900°C in air for 12 hours to finally obtain LiCo 0.98 Al 0.01 Mg 0.01 O 2 , a traditional high-voltage lithium cobalt oxide material.
对比例2Comparative Example 2
将硝酸钴、硫酸铝、硝酸镍和硫酸锰按照摩尔比为0.97:0.01:0.01:0.01的比例加入到去离子水中，加入碳酸钠和氨水分别作为沉淀剂和络合剂，调节pH为7～8，使其沉淀，对沉淀剂进行烧结和研磨获得(Co0.97Al0.01Ni0.01Mn0.01)3O4；然后将其与Li2CO3按照Li/Co摩尔比为1.01:1的比例进行混合后，在空气中900℃烧结12h，最终获得
LiCo0.97Al0.01Ni0.01Mn0.01O2的传统高电压钴酸锂材料。Cobalt nitrate, aluminum sulfate, nickel nitrate and manganese sulfate were added to deionized water in a molar ratio of 0.97:0.01:0.01:0.01, sodium carbonate and ammonia water were added as a precipitant and a complexing agent respectively, and the pH was adjusted to 7-8 to precipitate, and the precipitant was sintered and ground to obtain (Co 0.97 Al 0.01 Ni 0.01 Mn 0.01 ) 3 O 4 ; then it was mixed with Li 2 CO 3 in a Li/Co molar ratio of 1.01:1, and sintered at 900°C in air for 12 hours to finally obtain Traditional high voltage lithium cobalt oxide material LiCo 0.97 Al 0.01 Ni 0.01 Mn 0.01 O 2 .
对比例3Comparative Example 3
将硝酸钴、硫酸铝和硫酸镁加入到去离子水中，加入碳酸钠和氨水分别作为沉淀剂和络合剂，调节pH为7～8，使其沉淀，对沉淀剂进行烧结和研磨获得掺杂铝和镁的钴氧化合物；然后将其与Li2CO3按照Li/Co摩尔比为1.01:1的比例，并保证Co：Al：Mg：Ti摩尔比为0.97:0.01：0.01:0.01的比例与TiO2进行混合后，在空气中900℃烧结12h，最终获得LiCo0.97Al0.01Mg0.01Ti0.01O2的传统高电压钴酸锂材料。Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to precipitate, the precipitant is sintered and ground to obtain a cobalt oxide compound doped with aluminum and magnesium; then it is mixed with Li2CO3 according to a Li/Co molar ratio of 1.01:1 and a Co:Al:Mg:Ti molar ratio of 0.97:0.01:0.01:0.01 and TiO2 , and then sintered at 900°C in air for 12 hours to finally obtain a traditional high-voltage lithium cobalt oxide material of LiCo 0.97 Al 0.01 Mg 0.01 Ti 0.01 O 2 .
对比例4Comparative Example 4
将硝酸钴、硫酸铝和硫酸镁加入到去离子水中，加入碳酸钠和氨水分别作为沉淀剂和络合剂，调节pH为7～8，使其沉淀，对沉淀剂进行烧结和研磨获得掺杂铝镁的钴氧前驱体；然后将其与Li2CO3按照Li/Co摩尔比为1.01:1的比例进行混合，再与TiO2和ZrO2进行混合，保证Co：Al：Mg：Ti：Zr的摩尔比为0.96:0.01:0.01：0.01，在空气中900℃烧结12h，最终获得LiCo0.96Al0.01Mg0.01Ti0.01Zr0.01O2的传统高电压钴酸锂材料。Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to precipitate, the precipitant is sintered and ground to obtain an aluminum-magnesium doped cobalt oxide precursor; then it is mixed with Li2CO3 at a Li/Co molar ratio of 1.01: 1 , and then mixed with TiO2 and ZrO2 to ensure that the molar ratio of Co:Al:Mg:Ti:Zr is 0.96: 0.01 : 0.01 : 0.01 , and sintered at 900℃ in air for 12h to finally obtain LiCo0.96Al0.01Mg0.01Ti0.01Zr0.01O2 traditional high voltage lithium cobalt oxide material.
对比例5Comparative Example 5
将硝酸钴、硫酸铝和硫酸镁加入到去离子水中，加入碳酸钠和氨水分别作为沉淀剂和络合剂，调节pH为7～8，使其沉淀，对沉淀剂进行烧结和研磨获得掺杂铝镁的钴氧前驱体；然后将其与Li2CO3按照Li/Co摩尔比为1.01:1的比例进行混合，再与TiO2和Y2O3混合，保证Co：Al：Mg：Ti：Y为0.96:0.01:0.01：0.01的比例混合后，在空气中900℃烧结12h，最终获得LiCo0.96Al0.01Mg0.01Ti0.01Y0.01O2的传统高电压钴酸锂材料。Cobalt nitrate, aluminum sulfate and magnesium sulfate are added to deionized water, sodium carbonate and ammonia water are added as precipitant and complexing agent respectively, the pH is adjusted to 7-8 to make it precipitate, and the precipitant is sintered and ground to obtain an aluminum-magnesium doped cobalt oxide precursor; then it is mixed with Li2CO3 at a Li/Co molar ratio of 1.01:1, and then mixed with TiO2 and Y2O3 to ensure that the ratio of Co:Al:Mg:Ti:Y is 0.96:0.01:0.01:0.01, and then sintered at 900°C in air for 12 hours to finally obtain LiCo 0.96 Al 0.01 Mg 0.01 Ti 0.01 Y 0.01 O 2 , a traditional high-voltage lithium cobalt oxide material.
测试例1Test Example 1
锂离子全电池的制备Preparation of lithium-ion full battery
(1)正极片制备(1) Preparation of positive electrode
将正极材料、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照重量比
97:1.5:1.5进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌，直至混合体系成均一流动性的正极浆料；将正极浆料均匀涂覆于厚度为9～12μm的铝箔上，压实密度为4.0g/cm3；将上述涂覆好的铝箔在5段不同温度梯度的烘箱烘烤后，再将其在120℃的烘箱干燥8h，然后经过辊压、分切得到所需的正极片。The positive electrode material, the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black are mixed according to the weight ratio 97:1.5:1.5, add N-methylpyrrolidone (NMP), and stir under the action of a vacuum stirrer until the mixed system becomes a positive electrode slurry with uniform fluidity; the positive electrode slurry is evenly coated on an aluminum foil with a thickness of 9 to 12 μm, and the compaction density is 4.0 g/cm 3 ; the coated aluminum foil is baked in an oven with 5 different temperature gradients, and then dried in an oven at 120° C. for 8 hours, and then rolled and cut to obtain the required positive electrode sheet.
(2)负极片制备(2) Negative electrode preparation
将质量占比为96.9％的人造石墨负极材料，质量占比为0.1％的单壁碳纳米管(SWCNT)导电剂、质量占比为0.9％的导电炭黑(SP)导电剂、质量占比为0.8％的羧甲基纤维素钠(CMC)粘结剂及质量占比为1.3％的丁苯橡胶(SBR)粘结剂以湿法工艺制成浆料，涂覆于负极集流体铜箔的表面，经烘干(温度：85℃，时间：5h)、辊压和模切得到负极片。96.9% by mass of artificial graphite negative electrode material, 0.1% by mass of single-walled carbon nanotube (SWCNT) conductive agent, 0.9% by mass of conductive carbon black (SP) conductive agent, 0.8% by mass of sodium carboxymethyl cellulose (CMC) binder and 1.3% by mass of styrene-butadiene rubber (SBR) binder were made into slurry by a wet process, coated on the surface of the negative electrode current collector copper foil, and dried (temperature: 85°C, time: 5h), rolled and die-cut to obtain the negative electrode sheet.
(3)非水电解液制备(3) Preparation of non-aqueous electrolyte
在充满氩气的手套箱(水分<10ppm，氧分<1ppm)中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、丙酸丙酯(PP)以1.5:1:2的质量比混合均匀，在混合溶液中缓慢加入基于非水电解液总质量13wt.％的LiPF6，搅拌均匀得到非水电解液。In a glove box filled with argon (water content <10ppm, oxygen content <1ppm), ethylene carbonate (EC), propylene carbonate (PC) and propyl propionate (PP) were mixed at a mass ratio of 1.5:1:2, and 13wt.% of LiPF 6 based on the total mass of the non-aqueous electrolyte was slowly added to the mixed solution and stirred to obtain a non-aqueous electrolyte.
(4)隔膜的制备(4) Preparation of diaphragm
在厚度为5μm的聚乙烯基材。On a polyethylene substrate with a thickness of 5 μm.
(5)锂离子电池的制备(5) Preparation of lithium-ion batteries
将上述准备的正极片、隔膜、负极片通过卷绕得到未注液的裸电芯；将裸电芯置于外包装箔中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形、分选等工序，获得所需的锂离子电池。The positive electrode sheet, separator and negative electrode sheet prepared above are wound to obtain a bare battery cell without liquid injection; the bare battery cell is placed in an outer packaging foil, and the prepared electrolyte is injected into the dried bare battery cell. After vacuum packaging, standing, forming, shaping, sorting and other processes, the required lithium-ion battery is obtained.
测试实施例和对比例的正极材料的Li/Na的摩尔含量比m1；随后将所述正极材料组装成锂离子电池，将得到的锂离子电池成品保证循环次数N＜10的条件下，将满电或者半电状态下(电压＞3.5V)的电池按照0.1C倍率放电至3.0V后拆解电池，测试放电后的正极材料的Li/Na的摩尔含量比m2。测试结果见表1。The molar content ratio m1 of the positive electrode materials of the test examples and comparative examples was measured; the positive electrode materials were then assembled into lithium-ion batteries, and the obtained lithium-ion battery finished product was discharged to 3.0V at a rate of 0.1C under the condition that the number of cycles N was less than 10, and the battery was disassembled after the battery was fully charged or half-charged (voltage>3.5V) was discharged to 3.0V, and the molar content ratio m2 of the positive electrode materials after discharge was measured. The test results are shown in Table 1.
表1：实施例和对比例的正极材料的组成测试结果
Table 1: Composition test results of positive electrode materials of Examples and Comparative Examples
Table 1: Composition test results of positive electrode materials of Examples and Comparative Examples
试验例2Test Example 2
锂离子半电池的制备Preparation of lithium-ion half-cells
将上述实施例和对比例的正极材料、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照重量比97:1.5:1.5进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌，直至混合体系成均一流动性的正极浆料；将正极浆料均匀涂覆于厚度为9～12μm的铝箔上，压实密度为4.0g/cm3；将上述涂覆好的铝箔在5段不同温度梯度的烘箱烘烤后，再将其在120℃的烘箱干燥8h，然后经过辊压、分切得到所需的正极片；将正极极片和隔膜分别使用扣电冲片模具冲成直径为12mm和19mm，其中隔膜为20um厚的基材隔膜、电解液为上述全电池所提到的电解液型号、金属锂负极组装成扣式电池(电池规格型号为2025)。The positive electrode materials of the above embodiments and comparative examples, the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black were mixed in a weight ratio of 97:1.5:1.5, N-methylpyrrolidone (NMP) was added, and the mixture was stirred under the action of a vacuum stirrer until the mixture became a positive electrode slurry with uniform fluidity; the positive electrode slurry was evenly coated on an aluminum foil with a thickness of 9 to 12 μm, and the compaction density was 4.0 g/cm 3 ; the coated aluminum foil was baked in an oven with 5 different temperature gradients, and then dried in an oven at 120° C. for 8 h, and then rolled and cut to obtain the required positive electrode sheet; the positive electrode sheet and the diaphragm were punched into diameters of 12 mm and 19 mm respectively using a button punching die, wherein the diaphragm was a 20 μm thick substrate diaphragm, the electrolyte was the electrolyte model mentioned in the above full battery, and the metal lithium negative electrode was assembled into a button battery (battery specification model was 2025).
在3～4.55V的电压范围内，分别以0.1C、0.5C、1C倍率分别进行充
放电测试；并在在3～4.55V的电压范围内，以0.5C倍率充放电循环100周，测试电池的100T循环容量保持率。测试结果见表2。In the voltage range of 3 to 4.55V, the charging rate is 0.1C, 0.5C, and 1C respectively. Discharge test; and in the voltage range of 3 to 4.55V, charge and discharge cycles were performed at a rate of 0.5C for 100 cycles to test the 100T cycle capacity retention rate of the battery. The test results are shown in Table 2.
表2：实施例和对比例的正极材料的化学性能测试结果
Table 2: Chemical performance test results of positive electrode materials of Examples and Comparative Examples
Table 2: Chemical performance test results of positive electrode materials of Examples and Comparative Examples
从上述表2中可以看出，本申请的正极材料具有较高的容量、极高的倍率性能，以及良好的循环性能。具体地，所述极高的倍率性能是指其在高倍率下仍具有较高的容量，可以通过高倍率下容量与低倍率下容量的比值来进行描述，循环性能好可以通过多次循环后的容量与初始容量的比值即容量保持率来体现。As can be seen from Table 2 above, the cathode material of the present application has a high capacity, extremely high rate performance, and good cycle performance. Specifically, the extremely high rate performance means that it still has a high capacity at a high rate, which can be described by the ratio of the capacity at a high rate to the capacity at a low rate. The good cycle performance can be reflected by the ratio of the capacity after multiple cycles to the initial capacity, that is, the capacity retention rate.
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内
The above is an explanation of the implementation methods of the present application. However, the present application is not limited to the above implementation methods. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims (10)
- 一种正极材料，其中，所述正极材料的化学式为Lia-xNaxCo1-z1- z2M1 z1M2 z2O2，其中0<x≤0.1，0.8≤a≤1，0≤z1≤0.07，0≤z2≤0.07，0.001≤z1+z2≤0.07，M1为Al、Mg、Mn、Ni中的至少一种，M2为Ti、Zr、B、P、Y、La、Te、Nb、W中的至少一种；A positive electrode material, wherein the chemical formula of the positive electrode material is Li ax Na x Co 1-z1- z2 M 1 z1 M 2 z2 O 2 , wherein 0<x≤0.1, 0.8≤a≤1, 0≤z1≤0.07, 0≤z2≤0.07, 0.001≤z1+z2≤0.07, M 1 is at least one of Al, Mg, Mn, and Ni, and M 2 is at least one of Ti, Zr, B, P, Y, La, Te, Nb, and W;所述正极材料满足：m1>m2；其中，m1为所述正极材料在充放电前Li/Na的摩尔含量比；m2为所述正极材料按照0.1C倍率放电至3.0V后Li/Na的摩尔含量比。The positive electrode material satisfies: m1>m2; wherein m1 is the molar content ratio of Li/Na of the positive electrode material before charge and discharge; and m2 is the molar content ratio of Li/Na after the positive electrode material is discharged to 3.0V at a rate of 0.1C.
- 根据权利要求1所述的正极材料，其中，所述正极材料中值粒径为3～20μm。The positive electrode material according to claim 1, wherein the median particle size of the positive electrode material is 3 to 20 μm.
- 根据权利要求1所述的正极材料，其中，所述正极材料的比表面积为0.1～1.0m2/g。The positive electrode material according to claim 1, wherein the specific surface area of the positive electrode material is 0.1 to 1.0 m 2 /g.
- 根据权利要求1-3任一项所述的正极材料，其中，所述正极材料的晶相结构为P63mc相结构。The positive electrode material according to any one of claims 1 to 3, wherein the crystal phase structure of the positive electrode material is a P63mc phase structure.
- 根据权利要求1-3任一项所述的正极材料，其中，所述正极材料满足如下关系式：
C＝Ax+B；The positive electrode material according to any one of claims 1 to 3, wherein the positive electrode material satisfies the following relationship:
C = Ax + B;其中，C为正极材料的克容量，单位为mAh/g；x为正极材料中钠的摩尔含量；-50<A<-100；100<B<300，0<x≤0.1。Wherein, C is the gram capacity of the positive electrode material, in mAh/g; x is the molar content of sodium in the positive electrode material; -50<A<-100; 100<B<300, 0<x≤0.1. - 根据权利要求5所述的正极材料，其中，所述正极材料的克容量为196～240mAh/g。The positive electrode material according to claim 5, wherein the gram capacity of the positive electrode material is 196 to 240 mAh/g.
- 一种正极片，其中，所述正极片包括权利要求1-6任一项所述的正极材料。A positive electrode sheet, wherein the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 6.
- 根据权利要求7所述的正极片，其中，所述正极片包括正极集流体和涂覆在正极集流体一侧或两侧表面的正极活性物质层，所述正极活性物质层包括正极活性物质、导电剂和粘结剂；The positive electrode sheet according to claim 7, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer coated on one side or both sides of the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, a conductive agent and a binder;所述正极片中正极活性物质层的压实密度为3.5～4.5g/cm3。The compaction density of the positive electrode active material layer in the positive electrode sheet is 3.5 to 4.5 g/cm 3 .
- 一种电池，其中，所述电池包括权利要求1-6任一项所述的正极材料，或者所述电池包括权利要求7或8所述的正极片。A battery, wherein the battery comprises the positive electrode material according to any one of claims 1 to 6, or the battery comprises the positive electrode sheet according to claim 7 or 8.
- 根据权利要求9所述的电池，其中，所述电池在3～4.5V和3～4.55V 的截止电压下分别可以获得≥196mAh/g和≥208mAh/g的可逆容量。 The battery according to claim 9, wherein the battery has a voltage range of 3 to 4.5 V and a voltage range of 3 to 4.55 V. At the cut-off voltage of , reversible capacities of ≥196 mAh/g and ≥208 mAh/g can be obtained respectively.
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