CN115911610A - Anode lithium supplement material, preparation method and application thereof - Google Patents
Anode lithium supplement material, preparation method and application thereof Download PDFInfo
- Publication number
- CN115911610A CN115911610A CN202211449790.2A CN202211449790A CN115911610A CN 115911610 A CN115911610 A CN 115911610A CN 202211449790 A CN202211449790 A CN 202211449790A CN 115911610 A CN115911610 A CN 115911610A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- nickel
- lithium supplement
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 201
- 239000013589 supplement Substances 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000005416 organic matter Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000004185 ester group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 61
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- 239000004094 surface-active agent Substances 0.000 claims description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 29
- 239000002033 PVDF binder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- 239000007790 solid phase Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 26
- 238000005118 spray pyrolysis Methods 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- -1 polyoxyethylene Polymers 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 12
- 235000012000 cholesterol Nutrition 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- LIPIURJJRUOGSS-UHFFFAOYSA-N dodecyl hydrogen carbonate Chemical compound CCCCCCCCCCCCOC(O)=O LIPIURJJRUOGSS-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 229940062993 ferrous oxalate Drugs 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 4
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- IBVWKDVFDAWRFU-UHFFFAOYSA-L benzenesulfonate;nickel(2+) Chemical compound [Ni+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 IBVWKDVFDAWRFU-UHFFFAOYSA-L 0.000 claims description 3
- HCJWWBBBSCXJMS-UHFFFAOYSA-J copper;dilithium;tetrachloride Chemical compound [Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2] HCJWWBBBSCXJMS-UHFFFAOYSA-J 0.000 claims description 3
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims description 3
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 3
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229960005191 ferric oxide Drugs 0.000 claims 1
- 229960001781 ferrous sulfate Drugs 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 230000001502 supplementing effect Effects 0.000 description 9
- 125000005394 methallyl group Chemical group 0.000 description 8
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 208000028659 discharge Diseases 0.000 description 4
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- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- FPHVRPCVNPHPBH-UHFFFAOYSA-N 4-benzylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=CC=C1 FPHVRPCVNPHPBH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
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- 238000000265 homogenisation Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
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- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
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- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a positive electrode lithium supplement material, a preparation method and application thereof. The positive electrode lithium supplement material comprises a positive electrode lithium supplement agent and a hydrophobic layer coated on the surface of the positive electrode lithium supplement agent; the positive electrode lithium supplement agent is Li 2 NiO 2 And/or Li 5 FeO 4 (ii) a The hydrophobic layer is a continuous phase formed by uniformly mixing inorganic carbon and a micromolecular organic matter with a hydrophobic group; wherein, the hydrophobic group is selected from one or more of alkyl, ester group and polyoxyalkene group. According to the invention, a continuous phase formed by uniformly mixing inorganic carbon and a micromolecular organic matter with a hydrophobic group is used as a hydrophobic layer to coat the surface of the positive electrode lithium supplement agent, and the hydrophobic property of the hydrophobic group is utilized to weaken the alkalinity, so that the hydrophobic property and the air stability of the positive electrode lithium supplement material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode lithium supplement material, a preparation method and application thereof.
Background
Lithium ion batteries are widely used in the fields of consumer electronics, new energy passenger cars and large-scale power station energy storage due to their high energy density, green environmental protection and long service life. In the first charge and discharge stage of the lithium ion battery, the organic Electrolyte forms a Solid Electrolyte Interface (SEI) with lithium salt as a main component at the Interface of the negative electrode material. The formation of an SEI film is an irreversible process that permanently consumes large amounts of active lithium source from the positive electrode, resulting in a low first cycle coulombic efficiency (ICE), reducing the capacity and energy density of the lithium ion battery.
In order to solve the problem of active lithium consumption, researchers have conducted systematic analyses based on the "prelithiation" technique. The primary mechanism of "prelithiation" (also known as "prelithiation" or "lithium replenishment") is to add additional active lithium to the interior of the lithium ion battery to replenish the consumed lithium ions prior to operation of the battery. Lithium is supplemented to the electrode material through pre-lithiation, and irreversible lithium loss caused by SEI film formation is counteracted, so that the total capacity and energy density of the battery are ensured. The pre-lithiation technology comprises negative electrode lithium supplement, positive electrode lithium supplement, diaphragm lithium supplement and the like. The lithium supplementing mode of the negative electrode comprises lithium foil lithium supplementing, lithium powder lithium supplementing, lithium silicide powder lithium supplementing, lithium supplementing by an electrolytic lithium salt water solution and the like, but because the metal lithium is an alkali metal with high reaction activity, the metal lithium can react with water violently, the requirements on production and use environments are very high, and the conventional solvent, a binder, a heat treatment process and the like are incompatible, so that the two lithium supplementing processes of the negative electrode need to invest a large amount of capital to modify a production line and lithium supplementing equipment, and further the lithium supplementing of the negative electrode is still limited by the technical problem in the battery manufacturing process. Compared with the difficult and high-input negative electrode lithium supplement, the positive electrode lithium supplement is much simpler and more convenient, and the typical positive electrode lithium supplement process is that a small amount of high-capacity lithium supplement additive is added in the positive electrode homogenizing process, and redundant Li elements are extracted from high-capacity positive electrode materials in the charging process and are inserted into the negative electrode to supplement the irreversible capacity of the first charge and discharge. The lithium-supplemented positive electrode has the greatest industrial application prospect due to high safety and no need of changing the existing battery production process.
The perfect anode lithium supplement material needs to meet 4-point basic requirements: 1) The lithium removal potential is lower than the upper voltage limit of the anode material, and the lithium insertion potential is lower than the lower voltage limit of the anode material, namely the additive is required to carry out irreversible lithium removal in the working voltage of the battery; 2) The lithium supplement material should have high specific capacity and volumetric energy density to ensure efficient prelithiation; 3) The lithium supplement material is compatible with the current general manufacturing process and a battery system, namely the lithium supplement material and the decomposition product thereof are stable in the traditional electrolyte, and the performance deterioration of the lithium ion battery can not be caused; 4) Lithium supplement materials have good environmental stability, i.e., they need to be stable in air or in a drier environment. The lithium-supplementing material of the anode at present comprises a lithium-rich compound, a nano composite material based on conversion reaction, a binary lithium compound and the like, and Li is mainly used 2 NiO 2 、Li 5 FeO 4 、Li 2 MnO 3 、Li 6 CoO 4 、Li 6 MnO 4 、Li 5 ReO 6 Nanocomposites of Co and lithium salts (e.g. Li) 2 S/Co, liF/Co and Li 2 O/Co), etc., wherein Li 2 NiO 2 And Li 5 FeO 4 Is a very ideal lithium supplementing additive for the lithium ion cathode material, and can provide 2 Li and 5 Li in each mol theoretically + The specific capacity can reach 486mAh/g and 867mAh/g, and the first efficiency and the energy density of the lithium ion battery can be obviously improved by mixing a certain amount of lithium supplement materials into the traditional anode material.
Patent CN109301242A discloses a lithium ion battery anode lithium supplement material Li 5 FeO 4 The preparation method comprises the following steps: firstly, taking a lithium source compound, an iron source compound, a complexing agent and a solvent as raw materials, and mixing and reacting to prepare sol; then drying the sol to prepare xerogel; then ball milling the dry gel to obtain powder; then, under the protection of inert gas, the powder is subjected to low-temperature pretreatment, then is ground, is heated to high temperature, and is sintered to obtain the lithium ion battery anode lithium supplement material Li 5 FeO 4 (ii) a However, li prepared by the above preparation method 5 FeO 4 The safety performance of the battery is affected due to the uncontrollable residual alkali amount and hygroscopicity on the surface of the material. In the prior art Li 2 NiO 2 And Li 5 FeO 4 Both are synthesized under protective atmosphere and stored under vacuum or inert atmosphere because the two positive electrode lithium supplement agents are unstable in air. Li 2 NiO 2 And Li 5 FeO 4 Because of higher alkalinity, corrosivity and strong water absorbability, stronger agglomeration effect occurs among material particles, the problem of homogenization jelly to a certain extent exists in the use process, and the material particles are extremely easy to oxidize; in addition, gas may be generated during the pre-lithiation process, and if the reaction is not complete, the battery expands due to subsequent circulation, which affects the safety performance of the battery.
Therefore, the moisture content of the material must be strictly controlled during use, and once water is absorbed, a large amount of residual alkali is generated to wear the equipment. When the moisture content in the battery pole piece is higher (more than 600 ppm), more moisture can be diffused to the electrolyte and reacts with lithium salt in the electrolyte to generate extremely strong corrosive HF, so that the structure of the lithium ion battery is damaged, and the capacity of the battery is attenuated; especially during charging and discharging, the higher the HF content, the faster the cell decays. Therefore, the presence of high water content in the battery not only causes the decomposition of lithium salt in the electrolyte and has a certain corrosion damage effect on the positive and negative electrode materials and the current collector, but also causes the reduction of the cycle performance and the safety performance of the battery. For this reason, controlling the moisture content of the positive electrode lithium supplement material is an important technical barrier in the commercial application process thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a positive electrode lithium supplement material, a preparation method and application thereof. The invention uses the continuous phase formed by uniformly mixing inorganic carbon and micromolecule organic matter with hydrophobic group as hydrophobic layer to coat the anode lithium supplement agent (Li) 2 NiO 2 And/or Li 5 FeO 4 ) The alkalinity is weakened by utilizing the hydrophobic property of the hydrophobic groups, so that the hydrophobic property and the air stability of the positive electrode lithium supplement material are improved; according to the invention, a surfactant is attached to a material to induce porous sites, a high-purity and porous solid phase precursor is prepared according to a stoichiometric ratio by a sol-gel method, a liquid phase reaction system is homogeneous and reacts more sufficiently, the particle size of the synthesized material is small and uniform, nucleation crystallization is carried out by high-temperature sintering, and the nano-sized or micron-sized positive electrode lithium supplement agent (the particle size is 0.2-5 mu m) is obtained by crushing, no obvious agglomeration phenomenon exists in the particle size range, finally the positive electrode lithium supplement agent is dispersed in an organic solvent with hydrophobic organic matters, the hydrophobic organic matters are pyrolyzed but not carbonized completely by spray pyrolysis treatment, so that a continuous phase formed by uniformly mixing inorganic carbon and small molecular organic matters with hydrophobic groups is coated on the surface of the positive electrode lithium supplement agent in a hydrophobic layer manner, and the positive electrode lithium supplement material is obtained.
The anode lithium supplement material prepared by the invention not only has a porous structure, but also is beneficial to increasing the contact area between the material and electrolyte, effectively shortening the migration path of electrons and lithium ions, fully exerting the lithium supplement performance of the material and prolonging the service life of a lithium ion battery; the hydrophobic layer coated on the surface can not only keep the structural stability of the material, but also weaken the alkalinity and improve the air stability of the material, and improve the comprehensive performance of the material; in addition, the positive electrode lithium supplement material prepared by the method has small and uniform particle size, and is added into the positive electrode active material during homogenization to prepare the positive electrode piece, so that the capacity and the first coulombic efficiency of the positive electrode active material are improved.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode lithium supplement material, which adopts the following technical scheme:
a positive electrode lithium supplement material comprising: the lithium ion battery comprises a positive electrode lithium supplement agent and a hydrophobic layer coated on the surface of the positive electrode lithium supplement agent; the positive electrode lithium supplement agent is Li 2 NiO 2 And/or Li 5 FeO 4 ；
The hydrophobic layer is a continuous phase formed by uniformly mixing inorganic carbon and a micromolecular organic matter with a hydrophobic group;
wherein, the hydrophobic group is selected from one or more of alkyl, ester group and polyoxyalkene group.
In the above-mentioned positive electrode lithium supplement material, as a preferred embodiment, the hydrophobic layer is made of a hydrophobic organic material, and is coated on the surface of the positive electrode lithium supplement agent by spray pyrolysis treatment; the hydrophobic organic matter is selected from one or more of polyvinylidene fluoride (PVDF), polyoxyalkene copolymer, cholesterol dodecyl carbonate (cholesterol lauryl carbonate), methacrylate and polydiene; the polyoxyethylene olefin copolymer is preferably one or two of methyl allyl polyoxyethylene polyoxypropylene ether and allyl polyethylene glycol.
In the above positive electrode lithium-supplementing material, as a preferred embodiment, the hydrophobic organic substance is preferably a copolymer of polyvinylidene fluoride and a polyoxyalkylene.
In the above-described positive electrode lithium-supplementing material, as a preferred embodiment, the hydrophobic organic substance is preferably polyvinylidene fluoride and cholesterol dodecyl carbonate.
According to the invention, the hydrophobic organic matter is subjected to spray pyrolysis treatment in a spray dryer, the hydrophobic organic matter can be pyrolyzed but not completely carbonized by controlling the conditions of the spray pyrolysis treatment, at the moment, a continuous phase formed by uniformly mixing inorganic carbon and micromolecular organic matter with a hydrophobic group is coated on the surface of the positive electrode lithium supplement agent in a hydrophobic layer form, and then the positive electrode lithium supplement material is obtained, wherein the inorganic carbon can increase the conductivity of the positive electrode lithium supplement material and reduce the impedance; the hydrophobicity of the hydrophobic group can weaken the alkalinity, so that the hydrophobic property and the air stability of the positive electrode lithium supplement material are improved.
The hydrophobic organic matter is selected from organic matters with hydrophobic groups of hydrocarbon groups, ester groups and polyoxy alkenyl groups, and comprises the following components: one or more of polyvinylidene fluoride (PVDF), a polyoxyalkylene copolymer, cholesterol dodecyl carbonate (cholesterol lauryl carbonate), methacrylate, polydiene; particularly, when the specific PVDF and the specific poly (oxyalkylene) copolymer are selected as hydrophobic organic matters and the PVDF and the cholesterol dodecyl carbonate are selected as the hydrophobic organic matters, the prepared positive electrode lithium supplement material has excellent hydrophobic property, the saturated water absorption is less than 500ppm, and the positive electrode lithium supplement material with ppm-level hydrophobic capacity is realized.
In the above-mentioned positive electrode lithium-supplementing material, as a preferred embodiment, the particle size of the positive electrode lithium-supplementing material is 0.2 to 5 μm (e.g., 0.25 μm, 0.28 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm), and the thickness of the hydrophobic layer is 3 to 8nm (e.g., 4nm, 5nm, 6nm, 7 nm).
The particle size of the positive electrode lithium supplement material is limited to 0.2-5 mu m, and the positive electrode lithium supplement material is added into the positive electrode active material during homogenization in the particle size range to prepare a positive electrode piece, so that the capacity and the first coulombic efficiency of the positive electrode active material are improved; if the particle size of the positive electrode lithium supplement material is too large, no small particles are filled in the large particle stack, the void ratio is large, the tap density of the material is low, the lithium ion diffusion distance is short, and the first coulombic efficiency and the energy density of the battery are reduced; if the particle size of the positive electrode lithium supplement material is too small, the particles are easy to agglomerate due to high surface energy, so that the particles are uneven when mixed with the positive electrode active material, and side reactions are easy to occur on the surface, thereby reducing the capacity and the first coulombic efficiency of the battery.
In the above-mentioned positive electrode lithium supplement material, as a preferred embodiment, the positive electrode lithium supplement material has a porosity of 12% to 28% (e.g. 15%, 17%, 19%, 20%, 22%, 25%, 27%).
The porosity of the anode lithium supplement material is limited to 12% -28%, the contact area of the material and electrolyte is increased in the range, the migration path of electrons and lithium ions is effectively shortened, the full play of the lithium supplement performance of the material can be realized, and the service life of the lithium ion battery is further prolonged.
The second aspect of the present invention provides a preparation method of the above positive electrode lithium supplement material, including:
(1) Firstly, dissolving a surfactant in a solvent to obtain a surfactant solution, adding a lithium source and a compound containing M, stirring until the solvent is evaporated, and then grinding to obtain a solid-phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in inert gas, cooling, and crushing to obtain the anode lithium supplement agent;
(3) And (3) dissolving a hydrophobic organic matter in an organic solvent, adding the positive electrode lithium supplement agent obtained in the step (2), and performing spray pyrolysis treatment to obtain the positive electrode lithium supplement material.
According to the invention, firstly, a lithium source and a compound containing M are added into a surfactant solution, the solvent is completely evaporated through stirring treatment, then a solid phase precursor is obtained through grinding treatment, the surfactant can enhance the surface activation energy of the material, and further the ion bonding is induced in a liquid phase system to obtain the high-purity and porous solid phase precursor, and the liquid phase reaction system has the advantages of being homogeneous and more fully reacting; then sintering and crushing the solid-phase precursor to obtain the anode lithium supplement agent, wherein the solid-phase precursor is subjected to nucleation and crystallization under inert gas in the sintering process to grow into primary particles, and then crushing is carried out to uniformly disperse secondary agglomeration, so that the nano-or micron-grade anode lithium supplement agent (with the particle size of 0.2-5 mu m) is obtained, and the anode lithium supplement agent does not have an obvious agglomeration phenomenon in the particle size range; and finally, dispersing the positive electrode lithium supplement agent in an organic solvent with hydrophobic organic matters, and performing spray pyrolysis treatment to pyrolyze but not completely carbonize the hydrophobic organic matters, so that a continuous phase formed by uniformly mixing inorganic carbon and micromolecule organic matters with hydrophobic groups is coated on the surface of the positive electrode lithium supplement agent in the form of a hydrophobic layer to obtain a positive electrode lithium supplement material, and further the hydrophobic property and the air stability of the positive electrode lithium supplement material are improved.
In the above preparation method, as a preferred embodiment, in the step (1), the surfactant is selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, cetyltrimethylammonium bromide, polyvinylpyrrolidone, ethylene glycol, polyethylene glycol and oleylamine; preferably, the solvent is deionized water; preferably, the amount of the substance of the surfactant in the surfactant solution is in a concentration of 0.01 to 0.5mol/L (e.g., 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3 mol/L); preferably, the mass of the surfactant is 0.5 to 5% (e.g., 0.8%, 1%, 2%, 3%, 4%, 4.5%) of the mass of the M-containing compound.
According to the invention, the surface active agent is attached to the material to form porous sites, so that the anode lithium supplement material with a porous structure is prepared, the porous structure is favorable for increasing the contact area of the material and the electrolyte, the migration path of electrons and lithium ions is effectively shortened, the full play of the lithium supplement performance of the material can be realized, and the service life of the lithium ion battery is prolonged.
In the above production method, as a preferred embodiment, in the step (1), the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium metaborate, lithium molybdate, lithium sulfate, lithium tetrafluoroborate, lithium phosphate, lithium tetrachlorocuprate, lithium tetraborate, lithium oxalate, lithium acetate, lithium nitrate, lithium chloride, lithium fluoride, lithium chromate, and lithium trifluoromethanesulfonate; preferably, the lithium source is selected from one or more of lithium carbonate, lithium nitrate, lithium oxalate, lithium acetate and lithium hydroxide.
In the above production method, as a preferred embodiment, in the step (1), the M-containing compound is selected from an iron-containing compound and/or a nickel-containing compound; preferably, the iron-containing compound is selected from one or more of iron oxide, ferrous sulfate, ferrous chloride, iron phosphate, iron nitrate, ferrous oxalate, iron citrate and iron hydroxide; preferably one or more of ferric oxide, ferric nitrate, ferric phosphate, ferrous oxalate and ferrous chloride;
preferably, the nickel-containing compound is selected from the group consisting of nickel protoxide, nickel sesquioxide, nickel hydroxide, nickel oxyhydroxide (Ni (OH) 3 ) One or more of nickel carbonate, nickel nitrate, nickel oxalate, nickel acetate, nickel fluoride, nickel chloride, nickel bromide, nickel sulfate, nickel bis (hexafluoroethyl acetone), nickel sulfamate, nickel hydroxycarbonate, nickel acetylacetonate dihydrate, nickel trifluoromethanesulfonate, nickel benzenesulfonate, nickel acetylacetonate, and nickel fluoroborate; preferably one or more of nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous hydroxide, nickel oxalate, nickel carbonate, nickel acetate and nickel nitrate; preferably, the molar ratio of lithium element in the lithium source to M element in the M-containing compound is 2 to 5:1 (e.g. 2.5.
In the above production process, as a preferred embodiment, in the step (1), the temperature of the stirring treatment is 120 to 180 ℃ (e.g., 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃).
In the above production method, as a preferred embodiment, in the step (2), the conditions of the sintering treatment are: heating to 350-650 deg.C (such as 380 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 620 deg.C) at a heating rate of 5-20 deg.C/min (such as 6 deg.C/min, 8 deg.C/min, 10 deg.C/min, 15 deg.C/min, 18 deg.C/min), and maintaining for 6-18h (such as 8h, 10h, 12h, 15 h); the inert gas is nitrogen, argon or helium.
The invention limits the sintering temperature in the step (2) to 350-650 ℃, and the temperature is favorable for Li in the temperature range 2 NiO 2 And/or Li 5 FeO 4 Nucleating and crystallizing the material; if the sintering temperature is too low, the crystallization of the material is incomplete, more impurity phases are generated, the crystal structure integrity of the material is further caused, and the lithium ion extraction resistance is increased(ii) a If the sintering temperature is too high, the particles can continue to grow, the large particle size of the material can enable large particles to be accumulated without filling small particles, the void ratio is large, the tap density of the material is low, the lithium ion diffusion distance is short, and further the first coulomb efficiency and the energy density of the battery are reduced.
In the above-mentioned preparation method, as a preferable embodiment, in the step (2), the particle size of the positive electrode lithium supplement agent obtained by the pulverization treatment is 0.2 to 5 μm (for example, 0.25 μm, 0.28 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm).
The invention obtains primary particles with the particle size of 0.2-5 mu m through high-temperature crystallization growth, and the crushing treatment mainly has the function of uniformly dispersing secondary agglomeration.
In the above preparation method, as a preferred embodiment, in the step (3), the hydrophobic organic substance is one or more selected from polyvinylidene fluoride (PVDF), a polyoxyalkylene copolymer, cholesterol dodecyl carbonate (cholesterol lauryl carbonate), methacrylate, and polydiene; the polyoxyethylene olefin copolymer is selected from one or two of methyl allyl polyoxyethylene polyoxypropylene ether and allyl polyethylene glycol.
Preferably, the organic solvent is selected from one of ethanol, methanol and acetone; preferably, the mass of the hydrophobic organic substance is 0.5-2% (such as 0.6%, 0.7%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%) of the mass of the positive electrode lithium supplement agent; preferably, the mass ratio of the organic solvent to the positive electrode lithium supplement agent is 5-9:1-5 (such as 6.
According to the invention, the mass of the hydrophobic organic matter is limited to 0.5-2% of the mass of the positive lithium supplement agent, and a hydrophobic layer with the thickness of 3-8nm can be obtained in the range; if the mass of the added hydrophobic organic matter is too low, the hydrophobic property of the positive electrode lithium supplement material is not improved well; if the mass of the added hydrophobic organic matter is too high, the lithium ion deintercalation of the positive electrode lithium supplement material is hindered, the conductivity is reduced, and the organic matter remains too much on the surface of the positive electrode lithium supplement agent to cause gas generation in a battery system, which is not favorable for the safety performance of the battery.
In the above-mentioned production method, as a preferred embodiment, in the step (3), the spray pyrolysis treatment is carried out in a spray dryer under compressed air or an inert atmosphere at a temperature of 180 to 260 ℃ (e.g., 185 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃, 250 ℃).
The temperature of the spray pyrolysis treatment is limited to 180-260 ℃, and the hydrophobic organic matter can be pyrolyzed but not completely carbonized at the temperature, so that a continuous phase formed by uniformly mixing inorganic carbon and the micromolecule organic matter with hydrophobic groups is formed; if the temperature of the spray pyrolysis treatment is too low, the organic solvent is incompletely volatilized, so that the organic solvent remains on the surface of the material to influence the conductivity of the material, and the safety performance of the battery is not facilitated; if the temperature of the spray pyrolysis treatment is too high, the hydrophobic organic matter is too carbonized, the hydrophobic groups are too decomposed, and the hydrophobic performance of the material is poor.
A third aspect of the invention provides a positive electrode material comprising: a positive electrode active material and the positive electrode lithium supplement material or the positive electrode lithium supplement material prepared by the preparation method; preferably, the positive active material comprises lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt aluminate, lithium nickel cobalt manganate and a lithium-rich manganese-based positive material; preferably, the mass of the positive electrode lithium supplement material is 0.5% -5% (such as 1%, 2%, 3%, 4%, 4.5%) of the mass of the positive electrode active material.
The invention also provides a preparation method of the cathode material.
Compared with the prior art, the invention has the following advantages:
(1) The invention prepares the high-purity porous anode lithium supplement agent (with the grain diameter of 0.2-5 um) by a sol-gel method, the liquid phase reaction system is homogeneous and reacts more fully, and the synthesized material has small and uniform grain diameter, thereby being beneficial to the gram volume exertion of the material.
(2) According to the invention, the surface activity is attached to the material to induce porous sites, so that the full contact between the material and the electrolyte is improved, the migration path of electrons and lithium ions is effectively shortened, the full play of the lithium supplement performance of the material can be realized, and the service life of the lithium ion battery is prolonged.
(3) The invention takes the continuous phase formed by uniformly mixing inorganic carbon and micromolecule organic matter with hydrophobic group as a hydrophobic layer to coat the anode lithium supplement agent (Li) 2 NiO 2 And/or Li 5 FeO 4 ) The hydrophobicity of the hydrophobic group is utilized to weaken the alkalinity, so that the hydrophobicity and the air stability of the positive electrode lithium supplement material are improved, and the comprehensive performance of the material is further improved.
Drawings
Fig. 1 is an XRD pattern of the positive electrode lithium supplement material prepared in example 1 of the present invention;
fig. 2 is a TEM image of the positive electrode lithium supplement material prepared in example 1 of the present invention;
fig. 3 is a charge-discharge curve at 0.1C rate of a button cell assembled by the positive electrode lithium supplement material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiments of the present invention are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not indicate process parameters of specific conditions, and generally follow conventional conditions.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, all numerical values relating to amounts of components are "parts by weight" throughout, unless otherwise specified and/or indicated. The process parameters for the following examples, without specifying the particular conditions, are generally in accordance with conventional conditions. The starting materials described in the examples below are all commercially available from the open literature.
The specific embodiment of the invention provides a preparation method of a positive electrode lithium supplement material, which comprises the following steps:
(1) Firstly, weighing a surfactant (one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone, glycol, polyethylene glycol and oleylamine) and dissolving the surfactant in deionized water to prepare a 0.01-0.5mol/L surfactant solution, then adding a lithium source (lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium metaborate, lithium molybdate, lithium sulfate, lithium tetrafluoroborate, lithium phosphate, lithium tetrachlorocuprate, lithium tetraborate, lithium oxalate, lithium acetate, lithium nitrate, lithium chloride, lithium fluoride, lithium chromate and lithium trifluoromethanesulfonate), an iron source (one or more of iron oxide, ferrous sulfate, ferrous chloride, iron phosphate, ferric nitrate, ferrous oxalate, ferric citrate and ferric hydroxide) and/or a nickel source (one or more of nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous hydroxide, nickel carbonate, nickel nitrate, nickel oxalate, nickel acetate, nickel fluoride, nickel chloride, nickel bromide, nickel sulfate, nickel bis (hexafluoroethylacetone), nickel sulfamate, nickel hydroxycarbonate, nickel acetylacetonate dihydrate, nickel trifluoromethanesulfonate, nickel benzenesulfonate, nickel acetylacetonate and nickel fluoroborate), wherein the mass of the surfactant is 0.5 to 5% of the mass of the iron source and/or the lithium source is 2 to 5 mol% of the element of the iron source and/or the lithium source is 2 to 5mol ratio of the element of the iron source and/or the iron source to the nickel element of the nickel source: 1; stirring at 120-180 deg.c until the solvent is evaporated, and grinding to obtain solid phase precursor.
(2) And (3) putting the solid-phase precursor in an inert gas (nitrogen, argon, helium and the like) atmosphere, heating to 350-650 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 6-18h, cooling to room temperature, and crushing to obtain the anode lithium supplement agent (with the particle size of 0.2-5 um).
(3) Dissolving a hydrophobic organic matter (the hydrophobic organic matter is selected from one or more of (PVDF), a polyoxyalkene copolymer, cholesterol dodecyl carbonate, methacrylate and polydiene), and then adding the positive electrode lithium supplement agent obtained in the step (2), wherein the mass of the hydrophobic organic matter is 0.5-2% of that of the positive electrode lithium supplement agent, and the mass of the organic solvent is 5-9% of that of the positive electrode lithium supplement agent: 1-5; the anode lithium supplement material is obtained by carrying out spray pyrolysis (180-260 ℃) treatment in a spray dryer under compressed air or inert atmosphere.
The present invention will be described in further detail with reference to specific examples.
Embodiment 1 a method for preparing a positive electrode lithium supplement material, comprising:
(1) 4.2g of polyvinylpyrrolidone (M) are initially introduced w = 12000) is added into 250mL deionized water to obtain 0.014mol/L surfactant solution, then 120g lithium hydroxide and 143.9g ferrous oxalate are added into the surfactant solution, stirring treatment is carried out at 130 ℃ after mixing until the solvent is completely evaporated, and then grinding treatment is carried out to obtain a solid phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 10 hours; cooling and crushing to obtain the positive electrode lithium supplement agent Li with the average grain diameter of 0.4 mu m 5 FeO 4 ；
(3) 0.6g of PVDF and 0.6g of methallyl polyoxyethylene polyoxypropylene ether (M) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 210 ℃ in a spray dryer in a nitrogen atmosphere to obtain the positive electrode lithium supplement material.
FIG. 1 is an XRD (X-ray diffraction) pattern of a positive electrode lithium supplement material prepared in example 1 of the invention, which illustrates that a positive electrode lithium supplement agent Li is successfully prepared 5 FeO 4 ；
Fig. 2 is a TEM image of the positive electrode lithium-doped material obtained in example 1 of the present invention, and it can be seen from fig. 2 (b) that the thickness of the hydrophobic layer is 5nm.
The porosity of the positive electrode lithium supplement material prepared in example 1 was measured to be 24.7% by a nitrogen adsorption desorption method.
Embodiment 2 is a method for preparing a positive electrode lithium supplement material, including:
(1) 4.2g of polyvinylpyrrolidone (M) are initially introduced w = 12000) is added into 500mL deionized water to obtain 0.014mol/L surfactant solution, then 120g lithium hydroxide and 143.9g ferrous oxalate are added into the surfactant solution, stirring treatment is carried out at 130 ℃ after mixing until the solvent is completely evaporated, and then grinding treatment is carried out to obtain a solid phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 10 hours; cooling and crushing to obtain the positive electrode lithium supplement agent Li with the average grain diameter of 0.4 mu m 5 FeO 4 ；
(3) 1.2g of PVDF and 1.2g of methallyl polyoxyethylene polyoxypropylene ether (M) w = 3500) is dissolved in 500mL of ethanol, and then the positive lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 210 ℃ in a spray dryer in a nitrogen atmosphere to obtain the positive electrode lithium supplement material. Wherein the thickness of the hydrophobic layer is 8nm, and the porosity is 21.3%.
Embodiment 3 is a method for preparing a positive electrode lithium supplement material, including:
(1) Firstly, adding 9.3g of hexadecyl trimethyl ammonium bromide into 250mL of deionized water to obtain 0.1mol/L surfactant solution, then adding 50g of lithium hydroxide and 248.8g of nickel acetate tetrahydrate, mixing, stirring at 130 ℃ until the solvent is completely evaporated, and then grinding to obtain a solid-phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min,preserving the heat for 10 hours; cooling and crushing to obtain the positive electrode lithium supplement agent Li with the average grain diameter of 0.5 mu m 2 NiO 2 ；
(3) Dissolving 0.4g of PVDF and 0.4g of cholesterol dodecyl carbonate in 500mL of ethanol, and adding the positive lithium supplement agent Li obtained in the step (2) 2 NiO 2 93g, and then carrying out spray pyrolysis treatment at 230 ℃ in a spray dryer in a nitrogen atmosphere to obtain the positive electrode lithium supplement material, wherein the thickness of the hydrophobic layer is 4nm, and the porosity is 18.6%.
(1) Firstly, adding 7.2g of sodium dodecyl sulfate into 250mL of deionized water to obtain 0.1mol/L surfactant solution, then adding 202.0g of lithium oxalate and 92.7g of nickel hydroxide into the surfactant solution, mixing, stirring at 150 ℃ until the solvent is completely evaporated, and then grinding to obtain a solid-phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 8 hours; cooling and crushing to obtain the anode lithium supplement agent Li with the average grain diameter of 1.3 mu m 2 NiO 2 ；
(3) Dissolving 0.4g of PVDF and 0.4g of cholesterol dodecyl carbonate in 500mL of ethanol, and adding the positive lithium supplement agent Li obtained in the step (2) 2 NiO 2 93g, and then carrying out spray pyrolysis treatment at 230 ℃ in a spray dryer in a nitrogen atmosphere to obtain the positive electrode lithium supplement material, wherein the thickness of the hydrophobic layer is 5nm, and the porosity is 24.1%.
Example 5
Example 5 differs from example 1 in that 1.2g of PVDF was dissolved in 500mL of ethanol in step (3), and the lithium supplement agent Li for the positive electrode obtained in step (2) was further added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at 210 ℃ in a spray dryer in a nitrogen atmosphere to obtain a positive electrode lithium supplement material, wherein the rest is the same as the example 1, the thickness of a hydrophobic layer is 3nm, and the porosity is 19.3%.
Example 6
Example 6 differs from example 1 in that 1.2g of methallyl polyoxyethylene polyoxypropylene ether (M) is added in step (3) w = 3500) is dissolved in 500mL of ethanol, and then the positive lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at 210 ℃ in a spray dryer under nitrogen atmosphere to obtain the positive electrode lithium supplement material, wherein the rest is the same as the material in the example 1, the thickness of the hydrophobic layer is 3nm, and the porosity is 19.7%.
Comparative example 1 a method for preparing a positive electrode lithium supplement material, comprising:
(1) 4.2g of polyvinylpyrrolidone (M) are initially introduced w = 12000) is added into 250mL deionized water to obtain 0.014mol/L surfactant solution, then 120g lithium hydroxide and 143.9g ferrous oxalate are added into the surfactant solution, stirring treatment is carried out at 130 ℃ after mixing until the solvent is completely evaporated, and then grinding treatment is carried out to obtain a solid phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 10 hours; cooling and crushing to obtain the positive pole lithium supplement agent Li with the average grain diameter of 0.4 mu m 5 FeO 4 The porosity thereof was 21.5%.
Comparative example 2a method for preparing a positive electrode lithium supplement material, comprising:
(1) Firstly, adding 120g of lithium hydroxide and 143.9g of ferrous oxalate into 500mL of deionized water, mixing, stirring at 130 ℃ until the solvent is completely evaporated, and then grinding to obtain a solid-phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 10 hours; cooling and crushing to obtain the positive pole lithium supplement agent Li with the average grain diameter of 0.4 mu m 5 FeO 4 ；
(3) 0.6g of PVDF and 0.6g of methallyl polyoxyethylene polyoxypropylene ether (M) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 210 ℃ in a spray dryer under the nitrogen atmosphere to obtain the cathode lithium supplement material, wherein the thickness of a coating layer is 5nm, and the porosity is 13.2%.
Comparative example 3 a method for preparing a positive electrode lithium supplement material, comprising:
(1) 4.2g of polyvinylpyrrolidone (M) are initially introduced w = 12000) is added into 250mL deionized water to obtain 0.014mol/L surfactant solution, then 120g lithium hydroxide and 143.9g ferrous oxalate are added into the surfactant solution, stirring treatment is carried out at 130 ℃ after mixing until the solvent is completely evaporated, and then grinding treatment is carried out to obtain a solid phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 300 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 8 hours; cooling and crushing to obtain the positive electrode lithium supplement agent Li with the average particle size of 0.16 mu m 5 FeO 4 ；
(3) 0.6g of PVDF and 0.6g of methallyl polyoxyethylene polyoxypropylene ether (M) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 210 ℃ in a spray dryer under the nitrogen atmosphere to obtain the cathode lithium supplement material, wherein the thickness of a coating layer is 4nm, and the porosity is 20.8%.
Comparative example 4 a method for preparing a positive electrode lithium supplement material, comprising:
(1) 4.2g of polyvinylpyrrolidone (M) are initially introduced w = 12000) is added into 250mL deionized water to obtain 0.014mol/L surfactant solution, then 120g lithium hydroxide and 143.9g ferrous oxalate are added into the surfactant solution, stirring treatment is carried out at 130 ℃ after mixing until the solvent is completely evaporated, and then grinding treatment is carried out to obtain a solid phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in a nitrogen atmosphere, wherein the sintering conditions are as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 10 hours; cooling and crushing to obtain the positive electrode lithium supplement agent Li with the average grain diameter of 0.5 mu m 5 FeO 4 ；
(3) 0.14g of PVDF and 0.14g of methallyl polyoxyethylene polyoxypropylene ether (M) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 210 ℃ to obtain the cathode lithium supplement material, wherein the thickness of a coating layer is 3nm, and the porosity is 20.3%.
Comparative example 5
Comparative example 5 differs from example 1 in that 0.6g of PVDF and 0.6g of methallyl polyoxyethylene polyoxypropylene ether (M) were added in step (3) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at 150 ℃ in a spray dryer in a nitrogen atmosphere to obtain the anode lithium supplement material, wherein the thickness of a coating layer is 6nm, and the porosity is 17.2%.
Comparative example 6
Comparative example 6 differs from example 1 in that 0.6g of PVDF and 0.6g of methallyl polyoxyethylene polyoxypropylene ether (M) were added in step (3) w = 3500) is dissolved in 500mL ethanol, and then the positive electrode lithium supplement agent Li obtained in the step (2) is added 5 FeO 4 125g, and then carrying out spray pyrolysis treatment at the temperature of 300 ℃ in a spray dryer under the nitrogen atmosphere to obtain the anode lithium supplement material, wherein the thickness of a coating layer is 4nm, and the porosity is 19.6%.
Performance detection
Placing the positive electrode lithium supplement materials prepared in the examples 1-6 and the comparative examples 1-6 in an environment with the humidity of more than 80% for 24 hours at room temperature (25 +/-2 ℃), taking out and testing by using a Kaffi moisture meter to obtain the moisture content; mixing the positive electrode lithium supplement materials prepared in examples 1-6 and comparative examples 1-6 as active substances with polyvinylidene fluoride (PVDF) and superconducting carbon black (Super P) according to the mass ratio of 94; uniformly coating the slurry on a metal aluminum foil, vacuum drying at 80 ℃ for 2h, and finally cutting into pieces with the diameter of 14mm by using a punchThe circular pole piece is used as a working electrode; in a clean glove box (O) filled with Ar 2 The content is less than 0.1ppm 2 O content less than 0.1 ppm), a metal lithium sheet is taken as a counter electrode, a Celgard 2400 porous polypropylene film (PP) is taken as a diaphragm, and an electrolyte is 1mol/L lithium hexafluorophosphate (LiPF) 6 ) Solution, solvent Ethylene Carbonate (EC): ethyl carbonate (DMC) =1:1, preparing the R2032 type button cell according to a certain assembly process, and standing for 3 hours after the assembly process is finished so as to fully infiltrate the electrolyte and the electrode material. At room temperature (25 ℃ C. + -1), under the voltage range of 2.5-4.4V to Li/Li + Constant current charge and discharge experiments of the battery were performed, and the test results are shown in table 1.
The positive electrode lithium supplement materials prepared in examples 1 to 6 and comparative examples 1 to 6 are respectively blended with a positive electrode active material lithium iron phosphate to obtain a positive electrode material, wherein the positive electrode lithium supplement material accounts for 2% of the mass of the positive electrode active material, the positive electrode material is mixed with a binder PVDF and a conductive agent superconducting carbon black according to a mass ratio of 97.0 to 2.0, NMP is used as a solvent for ball milling for 60min to prepare a slurry, and then the slurry is uniformly coated on a metal aluminum foil to prepare a positive electrode sheet, artificial graphite is used as a negative electrode material, a tackifier is CMC, the binder is SBR, the conductive agent is SP, the mass ratio is 95.3.
TABLE 1
TABLE 2
Note: the capacity improvement rate means (actual capacity-3.0)/3.0 of the pouch batteries manufactured in each example and comparative example.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. A positive electrode lithium supplement material, comprising: the lithium ion battery comprises a positive electrode lithium supplement agent and a hydrophobic layer coated on the surface of the positive electrode lithium supplement agent; the positive electrode lithium supplement agent is Li 2 NiO 2 And/or Li 5 FeO 4 ；
The hydrophobic layer is a continuous phase formed by uniformly mixing inorganic carbon and a micromolecular organic matter with a hydrophobic group;
wherein, the hydrophobic group is selected from one or more of alkyl, ester group and polyoxyalkene group.
2. The positive lithium supplement material of claim 1, wherein the hydrophobic layer is prepared by coating a hydrophobic organic substance on the surface of the positive lithium supplement agent through spray pyrolysis; the hydrophobic organic matter is selected from one or more of polyvinylidene fluoride, poly-oxyalkylene copolymer, cholesterol dodecyl carbonate, methacrylate and polydiene; the polyoxyethylene olefin copolymer is preferably one or two of methyl allyl polyoxyethylene polyoxypropylene ether and allyl polyethylene glycol.
3. The positive lithium supplement material of claim 2, wherein the hydrophobic organic material is a copolymer of polyvinylidene fluoride and a polyoxy-olefin or the hydrophobic organic material is polyvinylidene fluoride and cholesterol dodecyl carbonate.
4. The positive electrode lithium supplement material according to any one of claims 1 to 3, wherein the particle size of the positive electrode lithium supplement material is 0.2 to 5 μm, and the thickness of the hydrophobic layer is 3 to 8nm; and/or the positive electrode lithium supplement material has a porosity of 12-28%.
5. A method for preparing a positive electrode lithium supplement material according to any one of claims 1 to 4, comprising:
(1) Firstly, dissolving a surfactant in a solvent to obtain a surfactant solution, adding a lithium source and a compound containing M, stirring until the solvent is evaporated, and then grinding to obtain a solid-phase precursor;
(2) Sintering the solid-phase precursor obtained in the step (1) in inert gas, cooling, and crushing to obtain a positive electrode lithium supplement agent;
(3) And (3) dissolving a hydrophobic organic matter in an organic solvent, adding the positive electrode lithium supplement agent obtained in the step (2), and performing spray pyrolysis treatment to obtain the positive electrode lithium supplement material.
6. The method according to claim 5, wherein in the step (1), the surfactant is one or more selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, cetyltrimethylammonium bromide, polyvinylpyrrolidone, ethylene glycol, polyethylene glycol and oleylamine; the solvent is deionized water; in the surfactant solution, the mass concentration of the surfactant is 0.01-0.5mol/L; the mass of the surfactant is 0.5-5% of that of the M-containing compound;
and/or the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium metaborate, lithium molybdate, lithium sulfate, lithium tetrafluoroborate, lithium phosphate, lithium tetrachlorocuprate, lithium tetraborate, lithium oxalate, lithium acetate, lithium nitrate, lithium chloride, lithium fluoride, lithium chromate and lithium trifluoromethanesulfonate;
and/or, the M-containing compound is selected from an iron-containing compound and/or a nickel-containing compound; the iron-containing compound is selected from one or more of ferric oxide, ferrous sulfate, ferrous chloride, ferric phosphate, ferric nitrate, ferrous oxalate, ferric citrate and ferric hydroxide; the nickel-containing compound is selected from one or more of nickel protoxide, nickelous trioxide, nickel hydroxide, nickelous hydroxide, nickel carbonate, nickel nitrate, nickel oxalate, nickel acetate, nickel fluoride, nickel chloride, nickel bromide, nickel sulfate, nickel bis (hexafluoroethyl acetone), nickel sulfamate, basic nickel carbonate, nickel acetylacetonate dihydrate, nickel trifluoromethanesulfonate, nickel benzenesulfonate, nickel acetylacetonate and nickel fluoroborate;
and/or the molar ratio of the lithium element in the lithium source to the M element in the M-containing compound is 2-5:1.
7. the production method according to claim 5 or 6, wherein in the step (1), the temperature of the stirring treatment is 120 to 180 ℃;
and/or in the step (2), the sintering treatment conditions are as follows: heating to 350-650 ℃ at the heating rate of 5-20 ℃/min, and keeping the temperature for 6-18h; the inert gas is nitrogen, argon or helium;
and/or in the step (2), the particle size of the positive electrode lithium supplement agent obtained by crushing treatment is 0.2-5 μm.
8. The method according to any one of claims 5 to 7, wherein in the step (3), the hydrophobic organic substance is selected from one or more of polyvinylidene fluoride, a polyoxyalkylene copolymer, cholesterol dodecyl carbonate, methacrylate, polydiene; the polyoxyalkylene copolymer is preferably one or two of methyl allyl polyoxyethylene polyoxypropylene ether and allyl polyethylene glycol;
and/or the organic solvent is selected from one of ethanol, methanol and acetone; the mass of the hydrophobic organic matter is 0.5-2% of that of the positive electrode lithium supplement agent; the mass ratio of the organic solvent to the positive electrode lithium supplement agent is 5-9:1-5.
And/or, the spray pyrolysis treatment is carried out in a spray dryer under compressed air or inert atmosphere at a temperature of 180-260 ℃.
9. A positive electrode material, comprising: a positive electrode active material and the positive electrode lithium supplement material according to any one of claims 1 to 4 or the positive electrode lithium supplement material produced by the production method according to any one of claims 5 to 8; the positive active material is selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt aluminate, lithium nickel manganese cobalt and a lithium-rich manganese-based positive material; the mass of the positive electrode lithium supplement material is 0.5-5% of the mass of the positive electrode active material.
10. Use of the positive electrode material of claim 9 in a lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116979051A (en) * | 2023-09-22 | 2023-10-31 | 深圳中芯能科技有限公司 | Manganese series lithium supplementing additive, preparation method and application thereof |
| CN116979018A (en) * | 2023-09-22 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Modified pole piece, preparation method thereof, secondary battery and power utilization device |
| CN117038938A (en) * | 2023-10-07 | 2023-11-10 | 深圳中芯能科技有限公司 | Positive electrode lithium supplementing agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116979051A (en) * | 2023-09-22 | 2023-10-31 | 深圳中芯能科技有限公司 | Manganese series lithium supplementing additive, preparation method and application thereof |
| CN116979018A (en) * | 2023-09-22 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Modified pole piece, preparation method thereof, secondary battery and power utilization device |
| CN116979051B (en) * | 2023-09-22 | 2023-12-01 | 深圳中芯能科技有限公司 | Manganese series lithium supplementing additive, preparation method and application thereof |
| CN117038938A (en) * | 2023-10-07 | 2023-11-10 | 深圳中芯能科技有限公司 | Positive electrode lithium supplementing agent and preparation method and application thereof |
| CN117038938B (en) * | 2023-10-07 | 2023-12-08 | 深圳中芯能科技有限公司 | Positive electrode lithium supplementing agent and preparation method and application thereof |
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