CN116505103A - Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery - Google Patents
Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery Download PDFInfo
- Publication number
- CN116505103A CN116505103A CN202310659133.9A CN202310659133A CN116505103A CN 116505103 A CN116505103 A CN 116505103A CN 202310659133 A CN202310659133 A CN 202310659133A CN 116505103 A CN116505103 A CN 116505103A
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- China
- Prior art keywords
- lithium
- agent
- supplementing agent
- supplementing
- material phase
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 263
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 247
- 239000000463 material Substances 0.000 claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 22
- 230000001603 reducing effect Effects 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 85
- 239000013589 supplement Substances 0.000 claims description 56
- 238000005253 cladding Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000010416 ion conductor Substances 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- 238000002955 isolation Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 38
- 239000003513 alkali Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 14
- 238000007600 charging Methods 0.000 abstract description 13
- 239000011162 core material Substances 0.000 description 105
- 239000011247 coating layer Substances 0.000 description 62
- 239000010410 layer Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
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- 238000000605 extraction Methods 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002120 nanofilm Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
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- 238000005056 compaction Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
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- 150000002506 iron compounds Chemical class 0.000 description 2
- 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 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
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- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
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- SRLSISLWUNZOOB-UHFFFAOYSA-N ethyl(methyl)azanide;zirconium(4+) Chemical compound [Zr+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C SRLSISLWUNZOOB-UHFFFAOYSA-N 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 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 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/13—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a lithium supplementing agent and a preparation method thereof, a positive electrode plate and a secondary battery, wherein the lithium supplementing agent comprises an inner core, the inner core comprises a first material phase, and the first material phase is Li 5a+2b Fe a M b O 4a+2b Wherein a is more than or equal to 0.5 and less than 1, b is more than or equal to 0 and less than or equal to 0.5, a+b=1, and M is a reducing metal element. The lithium supplementing agent can maintain a higher capacity level, is low in residual alkali number, is low in gas yield in the charging process, and improves the processing performance, the safety performance and the electrochemical performance of the lithium supplementing agent.
Description
Technical Field
The application relates to the technical field of energy, in particular to a lithium supplementing agent, a preparation method thereof, a positive pole piece and a secondary battery.
Background
In the first charge and discharge process of a battery such as a lithium ion secondary battery, a large amount of solid electrolyte interface film (SEI film) is generated on the surface of the negative electrode of the battery, so that limited lithium ions and electrolyte in the battery are consumed, irreversible capacity loss is caused, the coulomb efficiency of the lithium ion secondary battery is reduced, and the cycle life and the energy density of the lithium ion secondary battery are directly influenced. At present, the loss of the irreversible capacity can be eliminated by a method of supplementing lithium to the positive electrode, and the energy density and other electrical properties of the battery are improved. However, the existing lithium supplementing material has the problems of low capacity or high residual alkali number and high gas yield, is unfavorable for popularization and application of the lithium supplementing material, and limits the improvement of the performance of the lithium ion secondary battery.
Disclosure of Invention
The application provides a lithium supplementing agent, a preparation method thereof, a positive electrode plate and a secondary battery.
In a first aspect, the present application provides a lithium-supplementing agent comprising a core comprising a first material phase, the first material phase being Li 5a+2b Fe a M b O 4a+2b Wherein a is more than or equal to 0.5 and less than 1, b is more than or equal to 0 and less than or equal to 0.5, a+b=1, and M is a reducing metal element.
In the present application, the inner core of the lithium supplementing agent comprises a compound of the formula Li 5a+2b Fe a M b O 4a+2b Is low in O due to the addition of the reducing metal, li 5a+2b Fe a M b O 4a+2b The residual alkali number is lower, the gas yield is small in the charging process, and the processing performance, the safety performance and the electrochemical performance of the lithium supplementing agent are improved. In the application, the content of Fe is controlled to be larger than or equal to the content of M, so that the lithium supplementing agent can maintain a higher capacity level, and the stability of the lithium supplementing agent is improved while the lithium supplementing effect is ensured.
In an embodiment, the reducing metal element includes at least one metal element of divalent nickel, divalent manganese, divalent iron, and divalent cobalt. The divalent nickel element, divalent manganese element, divalent iron element, and divalent cobalt element can reduce Li 5a+ 2b Fe a M b O 4a+2b The oxygen content of the lithium supplementing agent is enabled to be small in gas yield in the charging process, and the safety performance and the electrochemical performance of the lithium supplementing agent are improved.
In one embodiment, the core further comprises a second material phase, the second material phase being Li 5 FeO 4 . The second material phase can improve the capacity of the lithium supplementing agent and realize better lithium supplementing effect.
In one embodiment, the second material phase is doped with the first material phase. The second material phase is mixed with the first material phase, so that the preparation of the lithium supplementing agent is facilitated.
In one embodiment, the second material phase fills the gaps of the first material phase. The compaction density of the lithium supplementing agent is improved, the capacity of the lithium supplementing agent is improved, and a better lithium supplementing effect is realized.
In one embodiment, the first material phase is bonded to an outer surface of the second material phase. Due to Li 5a+ 2b Fe a M b O 4a+2b Is higher than Li in residual alkali number 5 FeO 4 And the first material phase is coated on the outer surface of the second material phase, so that the residual alkali number of the whole lithium supplementing agent is reduced, and the processing performance and the safety performance of the lithium supplementing agent are improved.
In one embodiment, the core further comprises a third material phase, the third material phase being Li 2 MO 2 The third material phase is bonded to an outer surface of the first material phase. The third material phase can reduce the gas yield of the lithium supplementing agent and improve the safety performance and the electrochemical performance of the lithium supplementing agent.
In an embodiment, the lithium supplementing agent is further doped with a metal element, and the metal element comprises at least one of aluminum, titanium, zirconium, vanadium and manganese. The metallic elements such as aluminum, titanium, zirconium, vanadium, manganese, cerium and the like are doped in the lithium supplementing agent, so that the structural stability of the lithium supplementing agent can be improved, or the conductivity of the material can be improved.
In one embodiment, the lithium supplement has a surface residual base number of 0% to 1.5%.
In one embodiment, the lithium supplement has a particle size D50 of 0.5 μm to 38. Mu.m.
In one embodiment, the specific surface area of the lithium supplementing agent is 0.1m 2 /g-20m 2 /g。
In an embodiment, the lithium supplementing agent further comprises a coating layer, wherein the coating layer is positioned on the outer surface of the inner core, and the coating layer comprises at least one of an isolation coating layer, an ion conductor coating layer, an electronic conductor coating layer, a monoatomic deposition layer and an oxide nano film layer.
In an embodiment, the isolating coating layer includes at least one of a ceramic substance, a high molecular polymer, and a carbon material.
In one embodiment, the electronic conductor coating comprises at least one of a carbon material, a conductive polymer, or a conductive oxide.
In one embodiment, the material of the ion conductor coating layer includes at least one of perovskite type, NASICON type, garnet type or polymer type solid electrolyte.
In one embodiment, the mass ratio of the inner core to the coating layer is 100: (0.01-15).
In one embodiment, the thickness of the coating layer is 1nm to 400nm.
In one embodiment, the lithium supplement absorbs water at a rate of less than 20ppm/s in air at 25 ℃,30% -35% relative humidity.
In one embodiment, the lithium supplement absorbs water at a rate of less than 10ppm/s in air at 25 ℃,30% -35% relative humidity.
In one embodiment, the lithium supplement absorbs water at a rate of less than 10ppm/s in air at 25 ℃,20% -25% relative humidity.
In one embodiment, the lithium supplement absorbs water at a rate of less than 5ppm/s in air at 25 ℃,20% -25% relative humidity.
In a second aspect, the present application provides a method for preparing a lithium supplementing agent, the method for preparing a lithium supplementing agent comprising:
adding a lithium source, an iron source and an M source into the complexing agent solution, and stirring to obtain gel;
and sintering the gel in a protective atmosphere to obtain the inner core of the lithium supplementing agent.
Wherein the preparation method of the lithium supplementing agent is used for preparing the lithium supplementing agent.
In one embodiment, the method for preparing the lithium supplementing agent further comprises: and uniformly mixing the inner core and the coating substance, and sintering under a protective atmosphere to obtain the lithium supplementing agent.
In a third aspect, the present application provides a method for preparing a lithium supplementing agent, the method for preparing a lithium supplementing agent comprising:
mixing the solution of the iron source and the M source with the solution of the precipitant, and precipitating to obtain a precursor;
uniformly mixing a lithium source with the precursor, and sintering in a protective atmosphere to obtain the inner core of the lithium supplementing agent;
wherein the preparation method of the lithium supplementing agent is used for preparing the lithium supplementing agent.
In one embodiment, the method for preparing the lithium supplementing agent further comprises: and uniformly mixing the inner core with the coating substance, and sintering under a protective atmosphere to obtain the lithium supplementing agent.
In a fourth aspect, the present application provides a positive electrode sheet, where the positive electrode sheet includes the lithium supplementing agent as described above, or includes the lithium supplementing agent prepared by the preparation method of the lithium supplementing agent as described above.
In a fifth aspect, the present application provides a secondary battery comprising a negative electrode tab, a separator, and a positive electrode tab as described above.
In one embodiment, the secondary battery is a lithium ion battery, and in the lithium ion battery, the first lithium removal capacity of the lithium supplementing agent is greater than or equal to 550mAh/g.
In one embodiment, the lithium-supplementing agent has a first-cycle gas yield and a corresponding Li 5 FeO 4 The ratio of the first turn gas production is less than or equal to 50%.
Drawings
In order to more clearly describe the technical solutions in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.
Fig. 1 is a schematic structural diagram of a lithium supplementing agent according to an embodiment of the present application;
fig. 2 is an X-ray diffraction (XRD) pattern of a lithium supplement provided in an embodiment of the present application.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be made with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments.
The terms "first," "second," and the like herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
Furthermore, herein, the terms "upper," "lower," and the like, are defined with respect to the orientation in which the structure is schematically disposed in the drawings, and it should be understood that these directional terms are relative concepts, which are used for descriptive and clarity with respect thereto and which may be varied accordingly with respect to the orientation in which the structure is disposed.
For convenience of understanding, the following description will explain and describe english abbreviations and related technical terms related to the embodiments of the present application.
Relative humidity: refers to the percentage of water vapor pressure in air to saturated water vapor pressure at the same temperature.
ppm: i.e. parts per million, parts per million, ppm for gas, mole fraction or volume fraction, ppm for solution, mass concentration.
In the first charge and discharge process of a battery, such as a lithium ion secondary battery, a large amount of solid electrolyte interface film (SEI film) is generated on the surface of the negative electrode of the battery, and limited lithium ions and electrolyte in the battery are consumed, so that the capacity of the lithium ions is greatly reduced, and irreversible capacity loss is caused. In the first discharge, lithium ions extracted from the negative electrode are much smaller than those extracted from the positive electrode in the charge, resulting in a decrease in coulombic efficiency of the lithium ion secondary battery, directly affecting the cycle life and energy density of the lithium ion secondary battery. To solve this problem, the loss of the irreversible capacity can be eliminated by a method of supplementing lithium to the positive electrode, and the energy density and other electrical properties of the battery are improved. However, the existing lithium supplementing material has the problems of low capacity, high residual alkali number and high gas yield, is unfavorable for popularization and application of the lithium supplementing material, and limits the improvement of the performance of the lithium ion secondary battery.
Referring to fig. 1, the present application provides a lithium-supplementing agent 1, wherein the lithium-supplementing agent 1 includes a core 10, the core 10 includes a first material phase, and the first material phase is Li 5a+2b Fe a M b O 4a+2b Wherein a is more than or equal to 0.5 and less than 1, b is more than or equal to 0 and less than or equal to 0.5, a+b=1, and M is a reducing metal element.
Wherein Li represents a lithium element, fe represents an iron element, and O represents an oxygen element. The reducing metal is a metal having a reducing property, which is easily combined with oxygen, and which can suppress the generation of oxygen by the lithium supplementing material.
The lithium supplementing agent 1 is applied to the positive electrode of the battery to pre-lithiate the positive electrode, and lithium is added into the battery to supplement lithium ions before the battery works. In an embodiment, when the lithium-compensating agent 1 is applied, the lithium-compensating agent 1 may be coated on the outer surface of the positive electrode tab of the battery, or the lithium-compensating agent 1 may be embedded on the outer surface of the positive electrode tab of the battery. In other embodiments, the lithium supplementing agent 1 may be added during the preparation of the positive electrode sheet of the battery, so that the lithium supplementing agent 1 is dispersed on the outer surface and inside of the positive electrode sheet of the battery.
The lithium supplementing agent 1 comprises a core 10, wherein the core 10 has high lithium content, and lithium (Li) of the core 10 can be released and transferred to a battery cathode in the first charging process, so that irreversible lithium loss caused by formation of an SEI film is counteracted, and the total capacity and energy density of the battery are improved.
The lithium supplementing agent 1 provided by the application has high lithium supplementing capacity, less gas production in the charging process and higher safety performance.
In the prior art, lithium ferrite, lithium nickelate or lithium manganate is generally used as the lithium supplementing agent 1, when lithium ferrite (Li 5 FeO 4 ) When the lithium ferrite is used as the lithium supplementing agent 1, the capacity of lithium ferrite is high, but the gas production amount of the lithium ferrite is large in the charging process, the impedance of a battery is increased, the safety performance and the electrochemical performance of the battery are reduced, the residual alkali number of the lithium ferrite is high, the gel of slurry is easily caused in the slurry mixing process, the slurry mobility is poor, and the processing performance of the lithium supplementing agent 1 is seriously affected. And when lithium nickelate (e.g. Li 2 NiO 2 ) Or lithium manganate (e.g. Li 2 MnO 2 ) When the lithium supplementing agent 1 is used, although the gas yield of the lithium nickelate/lithium manganate in the charging process is small and the residual alkali value is low, the capacity of the lithium nickelate/lithium manganate is low, the lithium supplementing effect is poor, and the improvement of the battery performance is limited.
In the present application, the chemical formula of the first material phase in the lithium supplementing agent 1 is Li 5a+2b Fe a M b O 4a+2b ，Li 5a+2b Fe a M b O 4a+2b Can maintain a high capacity level, and reduce the activity of binding with water due to the addition of a reducing metal element, li 5a+ 2b Fe a M b O 4a+2b The residual alkali number is lower, the gas production amount is small in the charging process, and the processing performance, the safety performance and the electrochemical performance of the lithium supplementing agent 1 are improved. In the application, the content of Fe is controlled to be larger than or equal to the content of M, so that the stability of the lithium supplementing agent 1 can be improved while the lithium supplementing effect of the lithium supplementing agent 1 is ensured.
In one embodiment, a has a value in the range of 0.5.ltoreq.a.ltoreq.0.8. In this range, the residual alkali number of the lithium-ion replenishing agent 1 is lower, the gas yield is lower, the lithium-ion replenishing agent 1 has more excellent processability, safety performance and electrochemical performance, and the lithium-ion replenishing agent 1 has good lithium-ion replenishing effect and good stability.
In one embodiment, the reducing metal element includes at least one metal element of divalent nickel, divalent manganese, divalent iron, and divalent cobalt. Illustratively, when M is selected from Ni, the core 10 has the formula Li 5a+2b Fe a Ni b O 4a+2b . When M is selected from Mn, the core 10 has the formula Li 5a+2b Fe a Mn b O 4a+2b . When M is selected from Ni and Mn, the inner core 10 has the formula Li 5a+ 2b Fe a Ni b1 Mn b2 O 4a+2b Wherein b1+b2=b.
The divalent nickel element, divalent manganese element, divalent iron element, and divalent cobalt element can reduce Li 5a+2b Fe a M b O 4a+2b The gas yield in the charging process improves the safety performance and the electrochemical performance of the lithium supplementing agent 1.
In one embodiment, the inner core 10 further comprises a second material phase, the second material phase being Li 5 FeO 4 . The second material phase can improve the capacity of the lithium supplementing agent 1 and realize better lithium supplementing effect.
In one embodiment, the second material phase is doped with the first material phase. The second material phase is mixed with the first material phase, which is convenient for preparing the lithium supplementing agent 1.
In one embodiment, the second material phase fills the gaps of the first material phase. The compaction density of the lithium supplementing agent 1 is improved, the capacity of the lithium supplementing agent 1 is improved, and a better lithium supplementing effect is realized.
In one embodiment, the first material phase is bonded to the outer surface of the second material phase. Due to Li 5a+2b Fe a M b O 4a+2b Is higher than Li in residual alkali number 5 FeO 4 The first material phase is coated on the outer surface of the second material phase, so that the residual base number of the whole lithium supplementing agent 1 is reduced, and the processing performance and the safety performance of the lithium supplementing agent 1 are improved.
In one embodiment, the core 10 further includes a third material phase, the third material phase being Li 2 MO 2 The third material phase is bonded to the outer surface of the first material phase. The third material phase can reduce the gas production amount of the lithium supplementing agent 1 and improve the safety performance and the electrochemical performance of the lithium supplementing agent 1.
In one embodiment, the lithium supplementing agent 1 is further doped with a metal element, wherein the metal element comprises at least one of aluminum, titanium, zirconium, vanadium, manganese and cerium. The metallic elements such as aluminum, titanium, zirconium, vanadium, manganese, cerium and the like are doped in the lithium supplementing agent 1, so that the structural stability of the lithium supplementing agent 1 can be improved.
In one embodiment, the surface residual base number of the lithium supplement 1 is 0% -1.5%. The residual base number of the surface of the lithium supplementing agent 1 influences the processing performance and the stability of the lithium supplementing agent. It can be understood that the higher the residual base number of the surface of the lithium-supplementing agent 1, the stronger the alkalinity of the lithium-supplementing agent 1, the poor stability of the lithium-supplementing agent 1, and the lithium-supplementing agent 1 is easy to react with air and electrolyte, which directly affects the electrochemical performance of the lithium-supplementing agent 1 and reduces the safety performance of the battery. In addition, the surface residual alkali value of the lithium supplement agent 1 is high, the lithium supplement agent 1 is easy to cause gel of slurry in the slurry mixing process, the slurry fluidity is poor, and the processing performance of the lithium supplement agent 1 is seriously affected.
The surface residual alkali number of the lithium supplementing agent 1 is in the range of 0% -1.5%, the surface residual alkali number of the lithium supplementing agent 1 is low, the stability and the processing performance of the lithium supplementing agent 1 are improved, and the lithium supplementing agent 1 can realize the function of high-efficiency lithium supplementing.
In one embodiment, the surface residual base number of the lithium supplement 1 is 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, or 1.5%.
In one embodiment, the surface residual base number of the lithium supplement 1 is 0% -1%. Within this range, the performance of the lithium supplement 1 is more excellent. More preferably, the surface residual alkali value of the lithium supplementing agent 1 is 0% -0.5%.
In one embodiment, the particle size D50 of the lithium supplement 1 is 0.5 μm to 38. Mu.m. The particle diameter D50 is the particle diameter corresponding to the cumulative percentage of particle size distribution in the lithium-compensating agent 1 reaching 50%.
It can be understood that if the particle size of the lithium-supplementing agent 1 is too small, the lithium-supplementing agent 1 is liable to agglomerate, and lithium in the lithium-supplementing agent 1 is difficult to be extracted when the negative electrode is supplemented with active lithium, and the lithium-supplementing effect of the lithium-supplementing agent 1 is reduced; when the particle size of the lithium supplementing agent 1 is too large, the electron conduction and the ion conduction of the lithium supplementing agent 1 are not facilitated, the preparation of the slurry of the lithium supplementing agent 1 is not facilitated, and when the lithium supplementing agent 1 is coated on the positive electrode of a battery, aluminum foil is easily scratched due to the large particle size, so that the preparation of the positive electrode plate by the lithium supplementing agent 1 is not facilitated.
In the present embodiment, the particle diameter D50 of the lithium-supplementing agent 1 is controlled to be between 0.5 and 38 micrometers, so that the dispersibility of the lithium-supplementing agent 1 can be improved while the rapid extraction of lithium ions is ensured, and the use of the lithium-supplementing agent 1 and the protection of electrodes are facilitated.
In one embodiment, the particle size D50 of the lithium supplement 1 may be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm or 38 μm.
In one embodiment, the particle size D50 of the lithium supplement 1 is 3 μm to 15 μm. Within this range, the performance of the lithium supplement 1 is more excellent.
In one embodiment, the specific surface area of the lithium supplement 1 is 0.1m 2 /g-20m 2 And/g. In one embodiment, the specific surface area is measured by BET (Brunauer-Emmett-Teller) specific surface area, which is BET specific surface area. It is understood that if the specific surface area of the lithium-compensating agent 1 is too small, it is not advantageous to improve the conductivity and the lithium ion extraction and intercalation ability of the lithium-compensating agent 1. If the specific surface area of the lithium-compensating agent 1 is too large, the density of the lithium-compensating agent 1 is generally small, and the volumetric energy density is low.
In the present embodiment, the specific surface area of the lithium-supplementing agent 1 is controlled to be 0.1m 2 /g-20m 2 In the range of/g, not only the conductivity and the lithium ion extraction and intercalation ability of the lithium-ion-supplementing agent 1 but also the volumetric energy density of the lithium-supplementing agent 1 can be improved.
In one embodiment, the specific surface area of the lithium supplement 1 may be 0.1m 2 /g、0.5m 2 /g、1m 2 /g、2m 2 /g、3m 2 /g、4m 2 /g、5m 2 /g、6m 2 /g、7m 2 /g、8m 2 /g、9m 2 /g、10m 2 /g、11m 2 /g、12m 2 /g、13m 2 /g、14m 2 /g、15m 2 /g、16m 2 /g、17m 2 /g、18m 2 /g、19m 2 /g or 20m 2 /g。
In one embodiment, the lithium supplement 1 further includes a coating layer 20, and the coating layer 20 is located on the outer surface of the core 10. The cladding 20 may be entirely or partially coated on the outer surface of the core 10. The coating layer 20 can play a role in protecting the inner core 10, and it can be understood that if the coating layer 20 is not coated, and only the inner core 10 is used as the lithium supplement agent 1, on one hand, the outer surface of the inner core 10 has residual alkali, so that the stability of the lithium supplement agent 1 is reduced, and when the lithium supplement agent 1 is coated on a battery anode for use, the lithium supplement agent 1 is easier to cause gel of slurry in the slurry mixing process, the slurry fluidity is poor, and the processability of the lithium supplement agent 1 is affected. On the other hand, the surface of the lithium-compensating agent 1 generally contains a large amount of free lithium, and a high content of free lithium deteriorates the high-temperature storage performance of the battery, resulting in problems such as gas expansion and performance degradation during storage of the battery.
In the present application, on the one hand, the chemical formula of the inner core 10 is configured as Li 5a+2b Fe a M b O 4a+2b Under the condition of reducing the residual base number of the outer surface of the inner core 10, the coating layer 20 is arranged on the outer surface of the inner core 10, so that the residual base number of the lithium supplementing agent 1 is further reduced, and the stability and the processing performance of the lithium supplementing agent 1 are improved. On the other hand, the coating layer 20 reduces the free lithium content of the outer surface of the lithium-compensating agent 1, facilitating the storage of the lithium-compensating agent 1.
In one embodiment, the cladding layer 20 includes at least one of an isolation cladding layer 21, an ion conductor cladding layer 22, an electron conductor cladding layer 23, a monoatomically deposited layer, and an oxide nanomembrane layer.
In one embodiment, the cladding layer 20 is an isolation cladding layer 21. The insulating coating 21 can insulate the core 10 from moisture and carbon dioxide. The isolation coating layer 21 can protect the inner core 10, improve the stability of the inner core 10, ensure the lithium supplementing effect of the inner core 10, and simultaneously ensure the stability and the dispersion uniformity of the lithium supplementing agent 1 in the electrode active slurry and the active layer and good processing performance. The insulating coating 21 may be located on the outer surface of a part of the core 10, or may cover the entire outer surface of the core 10, which is not limited in this application.
In one embodiment, the insulating coating 21 includes at least one of a ceramic substance, a high molecular polymer, and a carbon material. Wherein the ceramic comprises at least one of alumina, silica, boehmite, silicon nitride, silicon carbide, and boron nitride. The polymer comprises one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethyl cellulose, polyacrylic acid, polyacrylate, polyacrylonitrile, polyamide, polyimide, polyvinylpyrrolidone, polyethylene oxide (PEO), polypyrrole (PPy), polytetrafluoroethylene (PTFE) and Polyurethane (PU). The carbon material comprises at least one of graphene, carbon nanotubes, carbon nanospheres, carbon nanofibers, graphite and carbon black.
In one embodiment, the coating 20 is an ion conductor coating 22. The ion conductor coating layer 22 can enhance the ion conductivity of the lithium-compensating agent 1. The ion conductor coating layer 22 is beneficial to the outward transportation of lithium ions in the lithium supplementing agent 1; at the same time, the ion conductor coating 22 also serves the auxiliary function of enhancing ion transport within the electrode. The ion conductor coating layer 22 may have a dense structure, may have a loose structure, may be entirely coated on the outer surface of the inner core 10, or may be partially coated on the outer surface of the inner core 10.
In one embodiment, the material of the ion conductor coating 22 includes at least one of perovskite type, NASICON type, garnet type, or polymer type solid state electrolytes. Wherein the perovskite type comprises Li 3x La 2/3-x TiO 3 (LLTO), in particular Li 0.5 La 0.5 TiO 3 、Li 0.33 La 0.57 TiO 3 、Li 0.29 La 0.57 TiO 3 、Li 0.33 Ba 0.25 La 0.39 TiO 3 、(Li 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01O3 、Li 0.5 La 0.5 Ti 0.95 Zr 0.05 O 3 At least one of the following. NASICON type such as but not limited to Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP). Garnet type comprises Li 7 La 3 Zr 2 O 12 (LLZO)、Li 6·4 La 3 Zr 1·4 Ta 0·6 O 12 ，Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 The polymer type solid electrolyte includes at least one of PEO/PPO/PVDF and the like in which lithium salts are dissolved.
In one embodiment, the cladding 20 is an electron conductor cladding 23. The electron conductor coating layer 23 can enhance the electron conductivity of the lithium-compensating agent 1. The electronic conductor coating layer 23 is advantageous in reducing the impedance inside the electrode, and at the same time, the electronic conductor coating layer 23 can also function as an auxiliary function of the conductive agent inside the electrode. The electron conductor coating layer 23 may have a dense structure, may have a loose structure, may be entirely coated on the outer surface of the inner core 10, or may be partially coated on the outer surface of the inner core 10.
In one embodiment, the electron conductor coating 23 comprises at least one of a carbon material, a conductive polymer, or a conductive oxide. The carbon material comprises at least one of graphene, carbon nano tubes, carbon nano spheres, carbon nano fibers, graphite and carbon black. The conductive polymer may be, but not limited to, the conductive polymer contained in the above-described insulating coating layer 21. The conductive oxide includes In 2 O 3 、ZnO、SnO 2 At least one of them.
In one embodiment, the cladding layer 20 is a deposited layer comprising a monoatomic deposited layer and/or an oxide nanomembrane layer obtained by atomic layer deposition techniques. In particular, the deposited layer may be a monoatomic deposited layer obtained by atomic layer deposition technique, and the hierarchy may be a monoatomic layer or a nanolayer constituted by atoms or molecules. Optionally, when the deposition layer is a monoatomic deposition layer, different atomic deposition agents can be selected according to different materials of the deposition layer, including but not limited to one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tetra (diethylamino) titanium, triethylsilane, tetraethylsilane and tetra (ethylmethylamino) zirconium.
Alternatively, the deposited layer may be an oxide nano-film layer. For example, the oxide nano-film layer may be a layer obtained by reacting the monoatomic deposition layer with oxygen, and the specific material is alumina, titania, silica, zirconia, etc. It is also possible to form the oxide layer of the nano-scale directly on the outer layer of the inner core by vapor deposition techniques. Of course, it is also possible to obtain the oxide nano-film layer by other techniques.
In one embodiment, the cladding layer 20 includes at least two of an isolation cladding layer 21, an ion conductor cladding layer 22, and an electron conductor cladding layer 23. Illustratively, in one embodiment, the cladding 20 comprises an isolation cladding 21 and an ion conductor cladding 22, and the ion conductor cladding 22 is coated on the outer surface of the core 10, and the isolation cladding 21 is coated on the outer surface of the ion conductor cladding 22.
In one embodiment, the cladding 20 includes an insulating cladding 21 and an electronic conductor cladding 23, and the insulating cladding 21 is coated on the outer surface of the core 10, and the electronic conductor cladding 23 is coated on the outer surface of the insulating cladding 21.
In one embodiment, the cladding 20 includes an isolation cladding 21, an ion conductor cladding 22, and an electron conductor cladding 23 (as shown in fig. 1), and the ion conductor cladding 22 is coated on the outer surface of the core 10, the isolation cladding 21 is coated on the outer surface of the ion conductor cladding 22, and the electron conductor cladding 23 is coated on the outer surface of the isolation cladding 21.
In an embodiment, when two or more kinds of the coating layers 20 are included in the coating layers 20, the coating order between the coating layers 20 may be set as needed, and is not limited to the above-listed types.
In one embodiment, the mass ratio of core 10 to cladding 20 is 100: (0.01-15). The mass ratio of the core 10 to the cladding 20 affects the performance of the lithium-compensating agent 1. If the content of the coating layer 20 is too low, the acting force of the coating layer 20 is weak, and the coating layer 20 is difficult to isolate the inner core 10 from the external environment, so that the effect of protecting the inner core 10 and improving the electron conductivity or the ion conductivity of the lithium-ion supplement agent 1 cannot be well achieved. If the content of the coating layer 20 is too high, the ratio of the lithium-compensating agent 1 in the positive electrode material is reduced, the lithium-compensating amount is further reduced, and the processing difficulty of the lithium-compensating agent 1 is also increased.
In the embodiment, the mass ratio of the core 10 to the coating layer 20 is controlled within the range of 100: (0.01-15), and the mass ratio of the coating layer 20 is proper, so that on one hand, the lithium supplementing agent 1 has better processing performance, and the binding force between the coating layer 20 and the core 10 is improved; on the other hand, the coating layer 20 does not excessively increase the mass of the lithium-compensating agent 1, and the energy density of the lithium-compensating agent 1 is not affected by the excessive mass of the coating layer 20, thereby reducing the capacity. In yet another aspect, the cladding 20 may better isolate the core 10 from the external environment to function to protect the core 10, and to increase the electronic or ionic conductivity of the lithium supplement 1.
In one embodiment, the mass ratio of core 10 to cladding 20 is 100:0.01, 100:0.05, 100:0.1, 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, or 100:15.
In one embodiment, the mass ratio of core 10 to cladding 20 is 100: (0.01-10). Within this range, the new energy of the lithium-supplementing agent 1 is more excellent, and more preferably, the mass ratio of the core 10 to the clad 20 is 100:0.01-5.
In one embodiment, the thickness of the cladding layer 20 is 1nm to 400nm. The thickness of the coating layer 20 affects the performance of the lithium-compensating agent 1. If the thickness of the coating layer 20 is small, it is difficult for the coating layer 20 to isolate the core 10 from the external environment, and thus the effect of protecting the core 10 and improving the electron conductivity or ion conductivity of the lithium-ion supplement agent 1 cannot be well achieved. If the thickness of the coating layer 20 is too large, the ratio of the lithium-compensating agent 1 in the positive electrode material is reduced, and the lithium-compensating amount is further reduced, and the interface resistance of the core 10 is also increased, thereby increasing the processing difficulty of the lithium-compensating agent 1.
In the present embodiment, the thickness of the coating layer 20 is controlled within the range of 1nm-400nm, and the thickness of the coating layer 20 is suitable, so that on one hand, the lithium supplementing agent 1 has better processability, and the binding force between the coating layer 20 and the inner core 10 is improved; on the other hand, the coating layer 20 does not excessively increase the mass of the lithium-compensating agent 1, and the energy density of the lithium-compensating agent 1 is not affected by the excessive mass of the coating layer 20, thereby reducing the capacity. In yet another aspect, the cladding 20 may better isolate the core 10 from the external environment to function to protect the core 10, and to increase the electronic or ionic conductivity of the lithium supplement 1.
In one embodiment, the thickness of the cladding layer 20 is 1nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, or 400nm.
In one embodiment, the rate of water absorption of the lithium supplement 1 in air at 25 ℃,30% -35% relative humidity is less than 20ppm/s. The rate of water absorption of the lithium-compensating agent 1 affects the processability and stability of the lithium-compensating agent 1. Generally, the greater the water absorption rate of the lithium-supplementing agent 1, the more rapidly the lithium-supplementing agent 1 absorbs water vapor in the air, the more easily the lithium-supplementing agent 1 is in contact reaction with the environmental water and a large amount of residual alkali is formed on the surface layer, so that the lithium-supplementing agent 1 is alkaline, and when the residual alkali is too high, the stability of the lithium-supplementing agent 1 is poor, and the lithium-supplementing agent 1 is easy to react with the air and the electrolyte, thereby directly affecting the electrochemical performance of the lithium-supplementing agent 1 and reducing the safety performance of the battery.
In the embodiment, the water absorption rate of the lithium supplement agent 1 in the air with the relative humidity of 30% -35% at 25 ℃ is smaller than 20ppm/s, the water absorption rate of the lithium supplement agent 1 is controlled to be lower, the lithium supplement agent 1 is ensured not to absorb the moisture in the air rapidly, the effective isolation of the lithium supplement agent 1 and water vapor is ensured, the stability of the inner core 10 is protected, the gram capacity exertion of the lithium supplement agent 1 is ensured, and the efficient lithium supplement is realized.
In one embodiment, the rate of water absorption of the lithium supplement 1 in air at 25℃and 30% -35% relative humidity is 20ppm/s, 19ppm/s, 18ppm/s, 17ppm/s, 16ppm/s, 15ppm/s, 14ppm/s, 13ppm/s, 12ppm/s, 11ppm/s, 10ppm/s, 9ppm/s, 8ppm/s, 7ppm/s, 6ppm/s, 5ppm/s, and the slurry is easily gelled during the size mixing process, and the fluidity of the slurry is poor, severely affecting the processability of the lithium supplement 1. 4ppm/s, 3ppm/s, 2ppm/s or 1ppm/s.
In one embodiment, the rate of water absorption of the lithium supplement 1 in air at 25 ℃, 30% -35% relative humidity is less than 10ppm/s. Under this condition, the performance of the lithium supplement 1 is more excellent.
In one embodiment, the rate of water absorption of the lithium supplement in air at 25 ℃,20% -25% relative humidity is less than 10ppm/s. The rate of water absorption of the lithium-compensating agent 1 affects the processability and stability of the lithium-compensating agent 1. In this embodiment, the water absorption rate of the lithium-supplementing agent 1 is controlled to be low, so that the lithium-supplementing agent 1 is ensured not to rapidly absorb moisture in the air, effective isolation between the lithium-supplementing agent 1 and water vapor is ensured, the stability of the inner core 10 is protected, and gram capacity exertion of the lithium-supplementing agent 1 is ensured, so that efficient lithium supplementation is realized.
In one embodiment, the rate of water absorption of the lithium supplement 1 in air at 25℃and 20% -25% relative humidity is 10ppm/s, 9ppm/s, 8ppm/s, 7ppm/s, 6ppm/s, 5ppm/s, 4ppm/s, 3ppm/s, 2ppm/s or 1ppm/s.
In one embodiment, the rate of water absorption of the lithium-compensating agent in air at 25 ℃,20% -25% relative humidity is less than 5ppm/s. Under this condition, the performance of the lithium supplement 1 is more excellent.
In one embodiment, the water absorption test method is as follows:
first, the room humidity is controlled at 25 ℃,20-25% or 30-35% relative humidity.
Second, 0.3-0.5g of the sample was taken out of the glove box, one sample at a time, and one sample was taken out of the glove box after the test.
Thirdly, placing the weighing bottle in an analytical balance with the precision of one ten thousandth, closing the cabin door and clearing.
Fourth, weighing 0.17-0.19 g of sample to be measured in the container, spreading the material out by a spoon, closing the cabin door, stabilizing for 3-5s, opening the timer, and recording the mass of the analytical balance as a value of 0 min. Next, values of 5, 10, 15, 20min were recorded, respectively, and average absorption data were calculated for 10-20 min.
The calculation formula is as follows:
units: ppm/s.
The application provides a preparation method of a lithium supplementing agent 1, wherein the preparation method of the lithium supplementing agent 1 is used for preparing the lithium supplementing agent 1, the preparation method of the lithium supplementing agent 1 comprises the following steps of S1-1 and S2-1, and the specific steps are as follows:
s1-1, adding a lithium source, an iron source and an M source into a complexing agent solution, and stirring to obtain gel;
And step S2-1, sintering the gel in a protective atmosphere to obtain the inner core 10 of the lithium supplementing agent 1.
In one embodiment, the method for preparing the lithium supplementing agent 1 further comprises the step S3-1: the core 10 and the coating material are uniformly mixed and sintered in a protective atmosphere to obtain the lithium supplementing agent 1.
Wherein the M source is a nickel source and/or a manganese source. In the step S1-1, a lithium source, an iron source and an M source are added into a complexing agent solution to prepare gel, and the lithium source, the iron source and the M source in the gel are uniformly mixed and have good dispersibility, so that an ordered structure is formed in the subsequent sintering. In one embodiment, the mixture of the lithium source, the iron source, the M source, and the complexing agent may be stirred under low temperature heating in step S1-1 to facilitate dissolution of the lithium source, the iron source, and the M source, and to evaporate at least a portion of the solution to facilitate formation of the gel. The heating temperature may be, for example, 60-90 ℃.
In step S2-1, the gel is sintered in a protective atmosphere to prevent the M source from being oxidized. In one embodiment, a shielding gas is introduced in step S2-1 to control the oxygen content to be 50ppm or less. The lithium source, the iron source and the M source react at high temperature to generate the chemical formula Li 5a+2b Fe a M b O 4a+2b Is provided for the core 10.
In step S3-1, the coating material is a material capable of forming the insulating coating layer 21, the ion conductor coating layer 22, and the electron conductor coating layer 23. The inner core 10 and the cladding material are sintered in a protective atmosphere to prevent oxidation of the M element. In one embodiment, a shielding gas is introduced in step S3-1 to control the oxygen content to be 50ppm or less.
In one embodiment, where the cladding material is carbon, the outer surface of the inner core 10 forms a carbon layer. The method for forming the carbon layer comprises the following steps: the inner core 20 is dispersed in a carbon source, and a carbon layer is formed on the surface of the inner core 20 after carbonization treatment.
It is noted that when the lithium-compensating agent 1 does not require the coating layer 20, the step S3-1 may be omitted.
In one embodiment, after the gel is obtained in step S1-1, the gel is dried, during the drying process, the iron compound is first separated out to form a seed crystal and grows into a core, after the gel is dried to a certain extent, the iron compound and the M compound are jointly separated out to form a coating layer, after the gel is dried, the gel is calcined at 300-700 ℃ to obtain a precursor, and the first material phase in the precursor is combined with the outer surface of the second material phase. In one embodiment, the preparation method of the lithium supplementing agent 1 further includes a step of doping a metal element, which is specifically as follows: crushing the obtained precursor, placing the crushed precursor into absolute ethyl alcohol, adding a surface doping element compound while stirring, drying while stirring, and calcining at 800 ℃ after drying to obtain the material core with the surface coated with the doping element.
The lithium supplementing agent 1 prepared by the method contains various heterogeneous elements, is high in purity, low in surface residual alkali number and high in lithium supplementing capacity, has a more stable structure, and can effectively reduce the release of oxygen species, so that the generation of gas is reduced. In addition, the coating layer on the surface of the lithium supplementing agent 1 can effectively isolate moisture, oxygen and the like from contacting the inner core 10, so that the structural stability of the lithium supplementing agent 1 is improved, a stable lithium supplementing effect is realized, and meanwhile, the electronic and ion conductivity of the lithium supplementing agent 1 can be improved, and the lithium ion extraction rate in the charging process is improved. The lithium supplementing agent 1 provided by the application has more excellent performance.
In one embodiment, the gel is sintered at a temperature of 400 ℃ to 1000 ℃ for a time period of 3 hours to 20 hours.
In one embodiment, the sintering temperature of the core 10 and the cladding material is 500-800 ℃ and the sintering time is 1-10 h.
In one embodiment, the lithium source is one or more of lithium oxide, lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, and lithium chloride.
In one embodiment, the iron source is one or more of iron acetate, iron nitrate, iron sulfate, iron hydroxide, iron chloride, and iron oxide.
In one embodiment, the manganese source is one or more of manganese acetate, manganese nitrate, manganese monoxide, manganese sulfate, manganese hydroxide, and manganese dichloride.
In one embodiment, the nickel source is one or more of nickel acetate, nickel nitrate, nickel oxide, nickel sulfate, nickel hydroxide, nickel chloride.
In one embodiment, the complexing agent is at least one of citric acid, ammonium citrate, maleic acid, oxalic acid, ammonium oxalate, ascorbic acid, polyethylene glycol, polyvinylpyrrolidone, glycerol, isopropanolamine, hydrogen peroxide, and the like.
In one embodiment, the complexing agent solution is a solution of complexing agent dissolved in a solvent, wherein the solvent is one or more of methanol, glycerol, ethanol, and water.
In one embodiment, the protective atmosphere is one or more of nitrogen, helium, argon, and neon.
The application provides a preparation method of a lithium supplementing agent 1, wherein the preparation method of the lithium supplementing agent 1 is used for preparing the lithium supplementing agent 1, the preparation method of the lithium supplementing agent 1 comprises the steps S1-2 and S2-2, and the specific steps are as follows:
s1-2, mixing the solution of an iron source and an M source with a precipitant solution, and precipitating to obtain a precursor;
step S2-2, after uniformly mixing a lithium source and a precursor, sintering the mixture in a protective atmosphere to obtain the inner core 10 of the lithium supplementing agent 1;
in one embodiment, the method for preparing the lithium supplementing agent 1 further comprises the step S3-2: and uniformly mixing the inner core 10 with the coating substance, and sintering under a protective atmosphere to obtain the lithium supplementing agent 1.
Wherein the M source is a nickel source and/or a manganese source. The solution of the iron source and the M source refers to a solution containing both the iron source and the M source. In step S1-2, the solution of the iron source and the solution of the M source are mixed with the precipitant solution, namely, the solution of the iron source and the solution of the M source are added into the precipitant solution to carry out precipitation reaction, or the precipitant solution is added into the solution of the iron source and the solution of the M source to carry out precipitation reaction. And filtering after precipitation reaction to obtain a solid precursor with an iron source and an M source which are uniformly mixed, wherein the precursor is an iron-based lithium supplementing material precursor containing M.
In the step S2-2, the lithium source and the precursor are uniformly mixed and sintered, and the lithium source reacts with iron and M to generate the chemical formula Li 5a+ 2b Fe a M b O 4a+2b Is provided for the core 10. Sintering in protective atmosphere can prevent M source from being oxidized. In one embodiment, a shielding gas is introduced in step S2-2 to control the oxygen content to be less than 50 ppm.
In step S3-2, the coating material is a material capable of forming the insulating coating layer 21, the ion conductor coating layer 22, and the electron conductor coating layer 23. The inner core 10 and the cladding material are sintered in a protective atmosphere to prevent oxidation of the M element. In one embodiment, a shielding gas is introduced in step S3-2 to control the oxygen content to be 50ppm or less.
The lithium supplementing agent 1 prepared by the method contains various heterogeneous elements, is high in purity, low in surface residual alkali number and high in lithium supplementing capacity, has a more stable structure, and can effectively reduce the release of oxygen species, so that the generation of gas is reduced. In addition, the coating layer on the surface of the lithium supplementing agent 1 can effectively isolate moisture, oxygen and the like from contacting the inner core 10, so that the structural stability of the lithium supplementing agent 1 is improved, a stable lithium supplementing effect is realized, and meanwhile, the electronic and ion conductivity of the lithium supplementing agent 1 can be improved, and the lithium ion extraction rate in the charging process is improved. The lithium supplementing agent 1 provided by the application has more excellent performance.
In one embodiment, the sintering temperature of the lithium source and the precursor is 600 ℃ to 1000 ℃ and the sintering time is 1h to 24h.
In one embodiment, the sintering temperature of the core 10 and the cladding material is 500-800 ℃ and the sintering time is 1-10 h.
In one embodiment, the lithium source is one or more of lithium oxide, lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, and lithium chloride. The iron source is one or more of ferric acetate, ferric nitrate, ferric sulfate, ferric hydroxide, ferric chloride and ferric oxide. The manganese source is one or more of manganese acetate, manganese nitrate, manganese monoxide, manganese sulfate, manganese hydroxide and manganese dichloride. The nickel source is one or more of nickel acetate, nickel nitrate, nickel oxide, nickel sulfate, nickel hydroxide and nickel chloride.
In one embodiment, the precipitant is at least one of ammonia water, sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, and calcium hydroxide.
The application provides a positive electrode plate, which comprises the lithium supplementing agent 1 or comprises the lithium supplementing agent 1 prepared by the preparation method of the lithium supplementing agent 1.
The application provides a secondary battery, which comprises a negative electrode plate, a diaphragm and a positive electrode plate.
In one embodiment, the secondary battery is a lithium ion battery in which the first delithiation capacity of the lithium supplement 1 is greater than or equal to 550mAh/g. The lithium supplementing agent 1 has higher first lithium removing capacity and can realize better lithium supplementing effect.
In one embodiment, with corresponding Li 5 FeO 4 The ratio of the first turn gas production is less than or equal to 50%. Compared with Li 5 FeO 4 The lithium supplementing agent 1 provided by the application has lower first-circle gas production rate and improves the safety performance and electrochemical performance of the battery.
In order to illustrate the beneficial effects of the methods of the present application, the present application also provides the following examples and comparative examples:
example 1
Example 1 provides a lithium-supplementing agent comprising a core and a coating layer, the core having the chemical formula Li 3.5 Fe 0.5 Ni 0.5 O 3 The coating layer is made of carbon material, and the mass ratio of the inner core to the coating layer is 100:5.
The preparation method of the lithium supplementing agent in the embodiment 1 comprises the following steps:
step 1, dissolving a citric acid complexing agent in an ethanol water solution, then dissolving according to the molar ratio of lithium hydroxide to iron acetate to nickel acetate=7:1:1, and stirring the solution at 60-90 ℃ until xerogel is formed.
And 2, sintering the xerogel prepared in the step 1 for 3-20 hours under the protective atmosphere at the temperature of 750 ℃ and with the oxygen content below 50ppm to prepare the inner core.
And 3, uniformly mixing the inner core prepared in the step 2 with a carbon source, and sintering at 300 ℃ in a protective atmosphere to obtain the lithium supplementing material.
Example 2
Example 2 provides a lithium-supplementing agent, which is different from example 1 in that in example 2, the chemical formula of the inner core of the lithium-supplementing agent is Li 3.8 Fe 0.6 Mn 0.4 O 3.2 。
Example 3
Example 3 provides a lithium-supplementing agent differing from example 1 in that in example 3, the chemical formula of the inner core of the lithium-supplementing agent is Li 4.4 Fe 0.8 Ni 0.2 O 3.6 。
Example 4
Example 4 provides a lithium-supplementing agent, which is different from example 1 in that in example 4, the inner core of the lithium-supplementing agent contains Li 3.5 Fe 0.5 Ni 0.5 O 3 Phase and Li 5 FeO 4 And (3) phase (C).
Example 5
Example 5 provides a lithium-supplementing agent differing from example 1 in that in example 5, the lithium-supplementing agent contains Li in the inner core 4.4 Fe 0.8 Ni 0.2 O 3.6 Phase and Li 2 NiO 2 And (3) phase (C).
Example 6
Example 6 provides a lithium-supplementing agent, which is different from example 1 in that in example 6, the inner core of the lithium-supplementing agent contains Li 4.4 Fe 0.8 Ni 0.2 O 3.6 Phase and Li 2 MnO 4 And (3) phase (C).
Example 7
Example 7 provides a lithium supplement which differs from example 1 in that in example 7 the mass ratio of core to coating is 100:15.
Example 8
Example 8 provides a lithium-supplementing agent, which is different from example 1 in structure in that the lithium-supplementing agent is doped with cerium as a metal element, a core is prepared by adopting a coprecipitation method in example 8, and the preparation method of the lithium-supplementing agent in example 8 comprises the following steps:
And step 1, dropwise adding ammonia water into the solution of iron acetate, nickel acetate and cerium acetate, carrying out heat treatment on the mixed solution, and carrying out precipitation reaction to generate the precursor of the Ni-containing iron-based lithium supplementing material.
And 2, uniformly mixing lithium hydroxide with the precursor of the iron-based lithium supplementing material containing M in the step 1 according to the molar ratio, performing sintering treatment at 600-1000 ℃ for 1-24 hours under the protection of protective atmosphere, and naturally cooling to finally obtain the core.
And step 3, uniformly mixing the inner core and a carbon source, and sintering for 1-10 hours at 500-800 ℃ under a protective atmosphere to obtain the lithium supplementing agent with the coating layer structure.
Comparative example 1
Comparative example 1 provides a lithium-supplementing agent differing from example 1 in the structure in that in comparative example 1, the core of the lithium-supplementing agent contains only a lithium-rich compound Li 5 FeO 4 。
Comparative example 2
Comparative example 2 provides a lithium-supplementing agent differing from example 1 in that in comparative example 2, the core of the lithium-supplementing agent contains only a lithium-rich compound Li 2.6 Fe 0.2 Ni 0.8 O 2.4 。
Comparative example 3
Comparative example 3 provides a lithium-supplementing agent differing from example 1 in the structure that in comparative example 3, the core of the lithium-supplementing agent contains only a lithium-rich compound Li 2 NiO 2 。
Comparative example 4
No lithium supplementing agent is added in the subsequent positive electrode plate.
The lithium supplementing agents provided in the above examples and comparative examples were assembled into a positive electrode sheet and a lithium ion battery, respectively, according to the following methods:
Positive plate: mixing a lithium supplementing agent and lithium iron manganese phosphate according to the mass ratio of 2:98 to obtain a mixture, and mixing the mixture with polyvinylidene fluoride and SP-Li according to the mass ratio of 95:3: mixing, ball milling and stirring according to the mass ratio of 2 to obtain positive electrode slurry, coating the positive electrode slurry on the surface of an aluminum foil, rolling, and vacuum drying at 110 ℃ overnight to obtain a positive electrode plate;
and (3) a negative electrode: a graphite negative electrode;
electrolyte solution: mixing ethylene carbonate and ethylmethyl carbonate in a volume ratio of 3:7, and adding LiPF 6 Electrolyte is formed, liPF 6 The concentration of (2) is 1mol/L;
a diaphragm: a polypropylene microporous separator;
and (3) assembling a lithium ion battery: and preparing the battery soft package.
Correlation performance test
1. Related testing of lithium supplementation
The lithium supplement core materials in the above examples 1 to 8 were subjected to X-ray diffraction (XRD) analysis, wherein the XRD pattern in example 1 is shown in fig. 2. As can be seen in FIG. 2, the lithium ferrite Li is contained in the lithium supplement core material 5 FeO 4 And lithium nickelate Li 2 NiO 2 And Li can be observed 5 FeO 4 And Li (lithium) 2 NiO 2 The diffraction peak is stronger and the intensity of the diffraction peak and the diffraction peak is equal, which indicates that the lithium supplementing agent core material contains a lithium rich compound Li 3.5 Fe 0.5 Ni 0.5 O 3 。
XRD of other examples also had corresponding characteristic diffraction peaks, respectively.
The electrochemical properties of each lithium ion battery assembled in the above lithium ion battery examples were respectively subjected to the performance test as in table 1, and the test conditions were as follows:
Constant-current constant-voltage charging, first-turn charging and discharging voltage is 2.0-4.3V, current is 0.1C, and cut-off current is 0.01C.
The correlation performance test results are shown in table 1 below:
TABLE 1 Performance test results
As can be seen from examples 1 to 8 and comparative example 1, the addition of the lithium supplementing agent can increase the first charge gram capacity of the battery, that is, the lithium supplementing agent provided in the present application can improve the battery performance.
As can be seen from examples 1-3 and comparative examples 1-3, the core includes Li in the present application 5a+2b Fe a M b O 4a+2b And the water absorption rate of the battery is lower when a is more than or equal to 0.5 and less than 1, b is more than or equal to 0 and less than or equal to 0.5, and a+b=1. When the value a is gradually increased, the first charge gram capacity of the battery is increased, the lithium supplementing gram capacity is greatly increased, the water absorption rate is reduced, and the gas yield is only slightly increased. In addition, examples 1-3 have lower gas production compared to comparative example 1. Whereas examples 1-3 have a higher gram capacity for lithium supplementation than comparative examples 2-3. In general, li provided herein 5a+2b Fe a M b O 4a+2b The comprehensive performance of the inner core is better, and the water absorption rate is lower, so that the battery has higher safety performance.
As can be seen from examples 1 and 4, the lithium supplement core increases Li 5 FeO 4 After the phase, the first charge gram capacity of the battery is increased, the lithium supplementing gram capacity is greatly improved, the water absorption rate is lower, and the gas production rate is not changed greatly. From this, the lithium-supplementing agent core increased Li 5 FeO 4 The phase is beneficial to improving the performance of the battery, in particular to improving the capacity of lithium supplementing gram and reducing the water absorption rate.
As can be seen from examples 3 and examples 5 to 6, the lithium-supplementing agent core increases Li 2 NiO 2 Phase or Li 2 MnO 4 After the phase, the gas yield of the battery is greatly reduced, the gram capacity and the water absorption rate of the first charge are not greatly changed, but a certain gram capacity of lithium supplement is lost. And Li is 2 MnO 4 The phase is capable of providing lower water uptake rates and gas production. From this, the lithium-supplementing agent core increased Li 2 NiO 2 Phase or Li 2 MnO 4 The phase is beneficial to reducing the gas yield of the battery.
As can be seen from examples 1 and 7, after increasing the thickness of the coating layer, the water absorption rate and gas production rate of the battery can be reduced to some extent, but the lithium supplementing gram capacity and the first charge gram capacity are reduced. Therefore, the thickness of the coating layer can be properly controlled, so that the water absorption rate and the gas production rate are reduced while the higher lithium supplementing gram capacity and the first charging gram capacity are ensured.
From examples 1 and 8, after cerium was doped in the lithium-supplementing agent, the lithium-supplementing agent after cerium doping had lower gas yield, although the water absorption rate, the lithium-supplementing gram capacity, and the first charge gram capacity of the battery were not greatly changed.
The lithium supplementing agent, the preparation method thereof, the positive electrode plate and the secondary battery provided by the embodiment of the application are described in detail, and specific examples are applied to illustrate the principle and the embodiment of the application, and the description of the embodiment is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have modifications in specific embodiments and application scope in accordance with the ideas of the present application, the present disclosure should not be construed as limiting the present application in view of the above description.
Claims (11)
1. A lithium supplementing agent is characterized by comprising a core, wherein the core comprises a first material phase, and the first material phase is Li 5a+2b Fe a M b O 4a+2b Wherein a is more than or equal to 0.5 and less than 1, b is more than or equal to 0 and less than or equal to 0.5, a+b=1, and M is a reducing metal element.
2. The lithium-supplementing agent according to claim 1, wherein the reducing metal element includes at least one metal element of divalent nickel, divalent manganese, divalent iron, and divalent cobalt.
3. The lithium supplement of claim 1, wherein the core further comprises a second material phase, the second material phase being Li 5 FeO 4 The second material phase is doped with the first material phase; or (b)
The second material phase fills the gaps of the first material phase; or (b)
The first material phase is bonded to an outer surface of the second material phase.
4. The lithium supplement of claim 1, wherein the core further comprises a third material phase, the third material phase being Li 2 MO 2 The third material phase is bonded to an outer surface of the first material phase.
5. The lithium-supplementing agent according to claim 1, wherein a metal element is further doped in the lithium-supplementing agent, and the metal element comprises at least one of aluminum, titanium, zirconium, vanadium, manganese and cerium.
6. The lithium-compensating agent of claim 1, further comprising a cladding layer on an outer surface of the core, the cladding layer comprising at least one of an isolation cladding layer, an ion conductor cladding layer, and an electron conductor cladding layer.
7. The lithium supplement of claim 6, wherein the lithium supplement has a surface residual base number of 0% -1.5%; and/or
The water absorption rate of the lithium supplementing agent in air with the relative humidity of 30-35% is less than 20ppm/s at 25 ℃; and/or
The rate of water absorption of the lithium supplement agent in air with 20-25% relative humidity is less than 10ppm/s at 25 ℃.
8. The preparation method of the lithium supplementing agent is characterized by comprising the following steps of: adding a lithium source, an iron source and an M source into the complexing agent solution, and stirring to obtain gel; sintering the gel in a protective atmosphere to obtain the inner core of the lithium supplementing agent; or (b)
The preparation method of the lithium supplementing agent comprises the following steps: mixing the solution of the iron source and the M source with the solution of the precipitant, and precipitating to obtain a precursor; and uniformly mixing a lithium source with the precursor, and sintering in a protective atmosphere to obtain the inner core of the lithium supplementing agent.
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises the lithium-supplementing agent according to any one of claims 1 to 7, or comprises the lithium-supplementing agent prepared by the preparation method of the lithium-supplementing agent according to claim 8.
10. A secondary battery comprising a negative electrode tab, a separator, and the positive electrode tab of claim 9.
11. The secondary battery according to claim 10, which is a lithium ion battery in which a lithium supplementing gram capacity of the lithium supplementing agent is 550mAh/g or more; and/or
The first circle gas yield of the lithium supplementing agent and corresponding Li 5 FeO 4 The ratio of the first turn gas production is less than or equal to 50%.
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| CN117154003A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, preparation method, sodium secondary battery and power utilization device |
| CN117712288A (en) * | 2024-02-02 | 2024-03-15 | 深圳海辰储能科技有限公司 | Positive pole piece, battery and electric equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117154003A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, preparation method, sodium secondary battery and power utilization device |
| CN117712288A (en) * | 2024-02-02 | 2024-03-15 | 深圳海辰储能科技有限公司 | Positive pole piece, battery and electric equipment |
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