CN116598483A - Positive electrode material, pole piece and preparation and application of lithium ion battery of positive electrode material and pole piece - Google Patents
Positive electrode material, pole piece and preparation and application of lithium ion battery of positive electrode material and pole piece Download PDFInfo
- Publication number
- CN116598483A CN116598483A CN202310726864.0A CN202310726864A CN116598483A CN 116598483 A CN116598483 A CN 116598483A CN 202310726864 A CN202310726864 A CN 202310726864A CN 116598483 A CN116598483 A CN 116598483A
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- CN
- China
- Prior art keywords
- lithium
- source
- manganese
- positive electrode
- battery
- Prior art date
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- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000010416 ion conductor Substances 0.000 claims abstract description 31
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 26
- 239000002738 chelating agent Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002322 conducting polymer Substances 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- -1 polypyridine Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002905 metal composite material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XMCTYDOFFXSNQJ-UHFFFAOYSA-N hexadecyl(methyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH2+]C XMCTYDOFFXSNQJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229960005191 ferric oxide Drugs 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000006104 solid solution Substances 0.000 abstract description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001253 polyvinylpolypyrrolidone Substances 0.000 description 1
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 1
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to an anode material, a pole piece and application of a lithium ion battery, wherein the chemical formula of the anode material of the battery is as follows: liMn 1‑ x Fe x PO 4 Wherein x is more than 0.1 and less than or equal to 0.7, and a coating layer is arranged on the surface of the battery anode material, and comprises a conductive polymer and a fast ion conductor. According to the nano lithium ferromanganese phosphate particles, the synthesized ferromanganese solid solution elements are controllable in proportion, uniform in phase and stable in structure, and lithium ions are smoothly extracted and intercalatedThe polarization resistance of the material is small; the uniform coating layer formed by self-polymerization of the organic monomers has controllable molecular weight, can improve the electronic conductivity of the material, can avoid damage caused by direct contact between the anode material and electrolyte, introduces a fast ion conductor material for double-phase continuous coating, can ensure the integrity of the material, can provide a fast channel of a lithium ion conductor, enhances the ion conductivity of the material, and improves the multiplying power performance and the cycle performance of the material.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a positive electrode material, a pole piece and application of the lithium ion battery.
Background
Based on the large-scale commercial application of lithium iron phosphate and the considerable application prospect of lithium manganese phosphate, researchers have formed mixed solid solutions in recent years by combining lithium iron phosphate and lithium manganese phosphate: lithium iron manganese phosphate (LiMn) 1-x Fe x PO 4 LMFP). The lithium iron manganese phosphate has the advantages of both the high energy density and the iron phosphateThe lithium has good cycle performance, and is a lithium ion battery anode material with very good use prospect. As a mixed solid solution of the two materials, lithium iron manganese phosphate has an olivine structure as well, and is composed of PO as in the lithium iron phosphate described above 4 Tetrahedrally linked Mn (Fe) O 6 And LiO 6 Octahedral composition. At present, a great deal of research has been explored to synthesize and modify lithium iron manganese phosphate and obtain remarkable effects, but little research has been conducted on the synergistic improvement of the electronic conductivity and the ionic conductivity of lithium iron manganese phosphate materials.
LiMn of olivine structure 1-x Fe x PO 4 There are two inherent drawbacks to materials. One is that the electron conductivity is low (-10) because the strong P-O bond limits the free movement of electrons -13 S/cm). Another is LiMn 1-x Fe x PO 4 The olivine structure of the material causes its Li + The diffusion channel being one-dimensional, relative to LiCoO of layered structure 2 And LiMn of tunnel structure 2 O 4 Li of it + The transmission rate is small (-10) -15 cm 2 /s)。
According to the application, the patent CN115498162A has the advantages that the specific capacity of the manganese iron lithium phosphate material double-coated by carbon and the germanium aluminum lithium phosphate is high, and better electrochemical performance can be exerted by the synergistic effect between the composite components, but the technology comprises the steps of coating amorphous carbon and then coating the fast ion conductor material germanium aluminum lithium phosphate, wherein the electron conductivity of the fast ion conductor on the outer layer is insufficient, so that the synergistic effect of the double-continuous-phase conductive ions cannot be realized;
the application patent CN109742340A prepares the nano-particle lithium iron manganese phosphate material by a hydrothermal method, and then sequentially adds the fast ion conductor element coating and the organic carbon source coating sintering, so that the discharge capacity and the cycle performance of the active material are effectively improved, but the hydrothermal method has high manufacturing cost and multiple coating and drying processes, so that the industrial application of the material is to be improved; patent CN115020685A of the application adopts Li 3 V 2 (PO 4 ) 3 The surface of the fast ion conductor material is coated, so that the lithium iron manganese phosphate material is prevented from being in direct contact with electrolyte, mn dissolution is reduced, and the material is improvedElectrochemical properties of the material, but fast ionic conductor Li 3 V 2 (PO 4 ) 3 The defects of high extraction difficulty, high energy consumption and high toxicity of the vanadium material precursor lead to that the technology is only remained in a laboratory.
Disclosure of Invention
Based on the above, it is necessary to provide a positive electrode material for sodium ion battery and sodium ion battery containing the same, aiming at the problems of the conventional positive electrode material.
In order to solve the technical problems, the application is realized by the following technical scheme:
a battery positive electrode material having the formula: liMn 1-x Fe x PO 4 Wherein x is more than 0.1 and less than or equal to 0.7, and a coating layer is arranged on the surface of the battery anode material, and comprises a conductive polymer and a fast ion conductor.
In one embodiment, the size of the battery anode material is 30-300 nm, the total thickness of the coating layer is 2-10 nm, and the mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10%, and the coating layer accounts for 1-5% of the mass of the battery anode material.
The preparation method of the battery anode material is used for preparing the battery anode material and comprises the following steps:
s1: weighing a lithium source, a manganese source, an iron source and a phosphorus source;
s2: adding a lithium source, a manganese source, an iron source and a phosphorus source into a solvent, fully stirring and dissolving, and then sequentially adding a dispersing agent and a chelating agent; stirring at constant temperature until the solvent evaporates to obtain a precursor material, transferring the precursor material to an inert atmosphere for high-temperature sintering, cooling and crushing to obtain a nano lithium iron manganese phosphate material;
s3: sequentially adding the ionic conductor and the conductive polymer monomer material, grinding and mixing the lithium manganese iron phosphate material, carrying out surface coating by high-temperature high-pressure spray drying, transferring to an inert atmosphere for sintering, cooling and crushing to obtain the bicontinuous phase coated lithium manganese iron phosphate composite material.
In one embodiment, in the step S1, the lithium source is at least one of lithium oxide, lithium carbonate, and lithium hydroxide; the manganese source is at least one of manganese dioxide, manganese phosphate and manganese oxalate; the iron source is at least one of ferric phosphate, ferric oxide, ferrous oxalate and ferric nitrate; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid; the dispersing agent is at least one selected from hexadecyl methyl ammonium bromide, sodium dodecyl sulfonate, polyvinylpyrrolidone and polyacrylamide; the chelating agent is at least one of a precipitation type chelating agent, a complexation type chelating agent, a phosphate type chelating agent and an organic polybasic phosphoric acid type chelating agent; the solvent includes at least one of ethanol, propanol, ethylene glycol, glycerol, and water.
In one embodiment, in the step S1, the stoichiometric ratio of the lithium source, the manganese source, the iron source, and the phosphorus source is 1.01 to 1.10:0.10 to 0.70:0.30 to 0.90:1.00; the added mass of the dispersing agent is 0.5-5.0% of the sum of the mass of the source manganese and the mass of the iron source; the added mass of the chelating agent is 2.0-10.0% of the sum of the mass of the manganese source and the mass of the iron source; in the step S2, the constant temperature is 80-150 ℃; the high-temperature sintering is carried out for 4-24 hours at 350-500 ℃, and the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas.
In one embodiment, in the step S3, a mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10, wherein the mass of the fast ion conductor material and the conductive polymer material accounts for 1-5% of the mass of the lithium iron manganese phosphate; the inlet temperature of the high-temperature high-pressure spray drying is 180-300 ℃, and the atomization pressure is 0.05-0.50 MPa; the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas; the sintering is carried out for 4-12 h at 450-650 ℃.
In one embodiment, in the step S3, the fast ion conductor is at least one of a lithium metal composite oxide, a lithium phosphorus composite compound, and a lithium boron composite compound; the electron conducting polymer is at least one of polyaniline, polypyrrole, polypyridine, polythiophene, poly-p-styreneylene and derivatives thereof, the PH value of the electron conducting polymer is 1-5, and the electron conducting polymer can be self-polymerized at high temperature.
In one embodiment, the lithium metal composite oxide has a chemical formula (Li 2 O)x-(MαO 2 )y-(NO 3 ) z, N element at least contains one or two of Al, ti, zr and Sn; the chemical formula of the lithium phosphorus compound is (Li 2 O)x-(MαO 2 )y-(PO 4 ) z; the chemical formula of the lithium boron complex compound is (Li 2 O)x-(MαO 2 )y-(BO 3 ) z, M is at least one selected from Ti, ge, la, zr, sr, al, Y, ta, W, nb, mn and yttrium, wherein x is more than or equal to 0.1 and less than or equal to 2.0,0.25, alpha is more than or equal to 4.0,0, y is more than or equal to 2.0,0.1 and z is more than or equal to 4.0.
The application of the battery anode material in the anode plate of the lithium ion battery is that the battery anode material is prepared by the preparation method.
A sodium ion battery is provided with the positive pole piece of the sodium ion battery.
In one embodiment, in the step S2, the acid anhydride is any one or a mixture of two or more of phthalic anhydride, acetic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride and adipic anhydride; the perovskite material A-site raw material is rare earth or alkaline earth metal element; the B-site raw material is a transition metal element; the lanthanum source is at least one of lanthanum hydroxide, lanthanum acetate, lanthanum nitrate hexahydrate, lanthanum carbonate, lanthanum acetylacetonate and lanthanum sulfate; the dispersing agent is at least one of polyethylene glycol, polyvinyl alcohol, polypyrrolidone and hexadecyl methyl ammonium bromide.
The advantages and effects:
1. the nanometer lithium iron manganese phosphate particles prepared by the liquid phase sol-gel method have smaller and concentrated grain size (about 30-300 nm), and the synthesized ferromanganese solid solution element has controllable proportion, uniform phase and stable structure, and the lithium ion deintercalation smoothness material has small polarization resistance.
2. The uniform coating layer formed by self-polymerization of the organic monomer has controllable molecular weight, and can be used as a surface conductive network layer to not only improve the electronic conductivity of the material, but also avoid the damage caused by direct contact between the anode material and electrolyte, inhibit the continuous growth of particles of the material in the high-temperature sintering process to a certain extent, effectively improve the gram-volume exertion of the material and reduce the internal resistance.
3. The rapid ion conductor material is introduced to carry out biphase continuous coating, so that not only can a framework structure be provided to ensure the integrity of the material, but also a rapid channel of a lithium ion conductor can be provided, the ion conductivity of the material is enhanced, lithium ions consumed during the formation of a solid electrolyte membrane and a positive electrolyte membrane are compensated, and the rate capability and the cycle performance of the material are improved.
Drawings
FIG. 1 is a schematic diagram of a lithium iron manganese phosphate composite material according to an embodiment of the present application;
FIG. 2 is a cycle chart and a 5C rate discharge chart according to an embodiment of the present application.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present application, the technical solutions of the embodiments of the present application will be clearly and completely described below 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, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It is to be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are merely for convenience in describing and simplifying the description based on the orientation or positional relationship shown in the drawings, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be construed as limiting the application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a 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, the meaning of "a plurality" or "a number" means two or more, unless specifically defined otherwise.
It should be understood that the structures, proportions, sizes, etc. shown in the drawings are for the purpose of understanding and reading the disclosure, and are not intended to limit the scope of the application, which is defined by the claims, but rather by the claims, unless otherwise indicated, and that any structural modifications, proportional changes, or dimensional adjustments, which would otherwise be apparent to those skilled in the art, would be made without departing from the spirit and scope of the application.
As shown in fig. 1-2, a battery positive electrode material, the chemical formula of which is: liMn 1-x Fe x PO 4 Wherein x is more than 0.1 and less than or equal to 0.7, and a coating layer is arranged on the surface of the battery anode material, and comprises a conductive polymer and a fast ion conductor.
The size of the battery anode material is 30-300 nm, wherein the total thickness of the coating layer is 2-10 nm, and the mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10%, and the coating layer accounts for 1-5% of the mass of the battery anode material. The nanometer lithium iron manganese phosphate particles prepared by the liquid phase sol-gel method have smaller and concentrated grain size (about 30-300 nm), and the synthesized ferromanganese solid solution element has controllable proportion, uniform phase and stable structure, and the lithium ion deintercalation smoothness material has small polarization resistance.
A method for preparing a battery positive electrode material for preparing the battery positive electrode material according to claim 2, comprising the steps of:
s1: weighing a lithium source, a manganese source, an iron source and a phosphorus source;
s2: adding a lithium source, a manganese source, an iron source and a phosphorus source into a solvent, fully stirring and dissolving, and then sequentially adding a dispersing agent and a chelating agent; stirring at constant temperature until the solvent evaporates to obtain a precursor material, transferring the precursor material to an inert atmosphere for high-temperature sintering, cooling and crushing to obtain a nano lithium iron manganese phosphate material;
s3: sequentially adding the ionic conductor and the conductive polymer monomer material, grinding and mixing the lithium manganese iron phosphate material, carrying out surface coating by high-temperature high-pressure spray drying, transferring to an inert atmosphere for sintering, cooling and crushing to obtain the bicontinuous phase coated lithium manganese iron phosphate composite material. The uniform coating layer formed by self-polymerization of the organic monomer has controllable molecular weight, and can be used as a surface conductive network layer to not only improve the electronic conductivity of the material, but also avoid the damage caused by direct contact between the anode material and electrolyte, inhibit the continuous growth of particles of the material in the high-temperature sintering process to a certain extent, effectively improve the gram-volume exertion of the material and reduce the internal resistance; meanwhile, the fast ion conductor material is introduced to carry out biphase continuous coating, so that not only can the framework structure be provided to ensure the integrity of the material, but also a fast channel of a lithium ion conductor can be provided, the ion conductivity of the material is enhanced, lithium ions consumed during the formation of a solid electrolyte membrane and a positive electrolyte membrane are made up, and the multiplying power performance and the cycle performance of the material are improved.
In step S1 of the embodiment of the present application, the lithium source is at least one of lithium oxide, lithium carbonate, and lithium hydroxide; the manganese source is at least one of manganese dioxide, manganese phosphate and manganese oxalate; the iron source is at least one of ferric phosphate, ferric oxide, ferrous oxalate and ferric nitrate; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid; the dispersing agent is at least one selected from hexadecyl methyl ammonium bromide, sodium dodecyl sulfonate, polyvinylpyrrolidone and polyacrylamide; the chelating agent is at least one of a precipitation type chelating agent, a complexation type chelating agent, a phosphate type chelating agent and an organic polybasic phosphoric acid type chelating agent; the solvent includes at least one of ethanol, propanol, ethylene glycol, glycerol, and water.
In the step S1 of the embodiment of the application, the stoichiometric ratio of the lithium source, the manganese source, the iron source and the phosphorus source is 1.01-1.10: 0.10 to 0.70:0.30 to 0.90:1.00; the added mass of the dispersing agent is 0.5-5.0% of the sum of the mass of the source manganese and the mass of the iron source; the added mass of the chelating agent is 2.0-10.0% of the sum of the mass of the manganese source and the mass of the iron source; in the step S2, the constant temperature is 80-150 ℃; the high-temperature sintering is carried out for 4-24 hours at 350-500 ℃, and the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas.
In step S3 of the embodiment of the present application, the mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10, wherein the mass of the fast ion conductor material and the conductive polymer material accounts for 1-5% of the mass of the lithium iron manganese phosphate; the inlet temperature of the high-temperature high-pressure spray drying is 180-300 ℃, and the atomization pressure is 0.05-0.50 MPa; the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas; the sintering is carried out for 4-12 h at 450-650 ℃.
In step S3 of the embodiment of the present application, the fast ion conductor is at least one of a lithium metal composite oxide, a lithium phosphorus composite compound, and a lithium boron composite compound; the electron conducting polymer is at least one of polyaniline, polypyrrole, polypyridine, polythiophene, poly-p-styreneylene and derivatives thereof, the PH value of the electron conducting polymer is 1-5, and the electron conducting polymer can be self-polymerized at high temperature. The total thickness of the coating layer of the lithium iron manganese phosphate composite material prepared by the method is about 2-10 nm, and the bicontinuous phase in-situ coating can form a more uniform and compact fast-conducting ion layer and a conductive layer; the fast ion conductor layer has a three-dimensional ion channel structure, so that the lithium ion and electron transmission rate in the electrochemical process can be promoted, the electrode reaction kinetics is improved, and the introduction of the polymer conductive layer is beneficial to accelerating the electron transmission rate, so that the polymer conductive layer has high specific capacity and excellent cycle performance.
The chemical formula of the lithium metal composite oxide of the embodiment of the application is (Li 2 O)x-(MαO 2 )y-(NO 3 ) z, N element at least contains Al, Ti. One or two of Zr and Sn; the chemical formula of the lithium phosphorus compound is (Li 2 O)x-(MαO 2 )y-(PO 4 ) z; the chemical formula of the lithium boron complex compound is (Li 2 O)x-(MαO 2 )y-(BO 3 ) z, M is at least one selected from Ti, ge, la, zr, sr, al, Y, ta, W, nb, mn and yttrium, wherein x is more than or equal to 0.1 and less than or equal to 2.0,0.25, alpha is more than or equal to 4.0,0, y is more than or equal to 2.0,0.1 and z is more than or equal to 4.0.
Use of a battery positive electrode material in a positive electrode sheet of a lithium ion battery, the battery positive electrode material being prepared by the preparation method of any one of claims 3-8.
A sodium ion battery having the sodium ion battery positive electrode sheet of claim 9. Specifically, examples are shown in table 1; the test data pairs for the inventive examples and comparative examples are shown in table 2.
Table 1 process parameters of the examples and comparative examples of the application
Table 2 comparative test data of examples and comparative examples according to the present application
The application of the battery anode material in the anode plate of the lithium ion battery is that the battery anode material is prepared by the preparation method.
Mixing the lithium manganese iron phosphate composite material with polyvinylidene fluoride (PVDF) and superconducting carbon black (SuperP) according to the mass ratio of 95.0:2.0:3.0, wherein N-methyl pyrrolidone (NMP) is used as the materialThe solvent is prepared into a positive plate, a metal lithium plate is a counter electrode, a Celgard2400 porous polypropylene film (PP) is a diaphragm, and the electrolyte is 1mol/L lithium hexafluorophosphate (LiPF) 6 ) Solution, solvent Ethylene Carbonate (EC): ethyl carbonate (DMC) =1: and (3) preparing the R2032 button cell by the mixed solution with the volume ratio of 1 according to a certain assembly process, and standing for 3h after the completion of the preparation to fully infiltrate the electrolyte and the electrode material. At room temperature (25 ℃ C.+ -. 1), at a voltage in the range of 2.5-4.3V, for Li/Li + And carrying out constant-current constant-voltage charge and discharge experiments.
Mixing a lithium manganese iron phosphate composite material with a binder PVDF and a conductive agent SP according to the mass ratio of 95.0:2.0:3.0, fully mixing NMP serving as a solvent, uniformly coating on a metal aluminum foil to prepare a positive electrode plate, taking artificial graphite as a negative electrode material, adding a tackifier CMC, taking a binder as SBR, taking a conductive agent as SP, preparing slurry according to the mass ratio of 95.3:1.2:1.5:2.0, uniformly coating on a metal copper foil to prepare a negative electrode plate, designing 1.15 coefficient according to the N/P ratio (gram volume of a negative electrode active substance x gram volume of a positive electrode active substance x content ratio of a positive electrode active substance), and assembling into a soft-packed full battery with the volume of 2.0Ah, and performing constant-current constant-voltage charge and discharge (charging with 1C constant current to 4.3V in a voltage range of 2.5-4.3V at room temperature (25 ℃ +/-1C) and then performing charging with 0.05 to a small current at a voltage of a platform of 4.3V).
A lithium ion battery is provided, wherein the lithium ion battery is provided with the positive pole piece of the sodium ion battery.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. A battery positive electrode material, characterized by the formula: liMn 1-x Fe x PO 4 Wherein x is more than 0.1 and less than or equal to 0.7, and a coating layer is arranged on the surface of the battery anode material, and comprises a conductive polymer and a fast ion conductor.
2. The positive electrode material of the sodium ion battery according to claim 1, wherein the size of the positive electrode material of the battery is 30-300 nm, the total thickness of the coating layer is 2-10 nm, and the mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10%, and the coating layer accounts for 1-5% of the mass of the battery anode material.
3. A method for preparing a battery positive electrode material for preparing the battery positive electrode material according to claim 2, comprising the steps of:
s1: weighing a lithium source, a manganese source, an iron source and a phosphorus source;
s2: adding a lithium source, a manganese source, an iron source and a phosphorus source into a solvent, fully stirring and dissolving, and then sequentially adding a dispersing agent and a chelating agent; stirring at constant temperature until the solvent evaporates to obtain a precursor material, transferring the precursor material to an inert atmosphere for high-temperature sintering, cooling and crushing to obtain a nano lithium iron manganese phosphate material;
s3: sequentially adding the ionic conductor and the conductive polymer monomer material, grinding and mixing the lithium manganese iron phosphate material, carrying out surface coating by high-temperature high-pressure spray drying, transferring to an inert atmosphere for sintering, cooling and crushing to obtain the bicontinuous phase coated lithium manganese iron phosphate composite material.
4. The method according to claim 3, wherein in the step S1, the lithium source is at least one of lithium oxide, lithium carbonate, and lithium hydroxide; the manganese source is at least one of manganese dioxide, manganese phosphate and manganese oxalate; the iron source is at least one of ferric phosphate, ferric oxide, ferrous oxalate and ferric nitrate; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid; the dispersing agent is at least one selected from hexadecyl methyl ammonium bromide, sodium dodecyl sulfonate, polyvinylpyrrolidone and polyacrylamide; the chelating agent is at least one of a precipitation type chelating agent, a complexation type chelating agent, a phosphate type chelating agent and an organic polybasic phosphoric acid type chelating agent; the solvent includes at least one of ethanol, propanol, ethylene glycol, glycerol, and water.
5. The method according to claim 3, wherein in the step S1, the stoichiometric ratio of the lithium source, the manganese source, the iron source and the phosphorus source is 1.01 to 1.10:0.10 to 0.70:0.30 to 0.90:1.00; the added mass of the dispersing agent is 0.5-5.0% of the sum of the mass of the source manganese and the mass of the iron source; the added mass of the chelating agent is 2.0-10.0% of the sum of the mass of the manganese source and the mass of the iron source; in the step S2, the constant temperature is 80-150 ℃; the high-temperature sintering is carried out for 4-24 hours at 350-500 ℃, and the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas.
6. The method according to claim 3, wherein in the step S3, a mass ratio of the fast ion conductor material to the conductive polymer material is 1: 1-10, wherein the mass of the fast ion conductor material and the conductive polymer material accounts for 1-5% of the mass of the lithium iron manganese phosphate; the inlet temperature of the high-temperature high-pressure spray drying is 180-300 ℃, and the atomization pressure is 0.05-0.50 MPa; the inert atmosphere is nitrogen, argon, helium or hydrogen-argon mixed gas; the sintering is carried out for 4-12 h at 450-650 ℃.
7. The method according to claim 3, wherein in the step S3, the fast ion conductor is at least one of a lithium metal composite oxide, a lithium phosphorus composite compound, and a lithium boron composite compound; the electron conducting polymer is at least one of polyaniline, polypyrrole, polypyridine, polythiophene, poly-p-styreneylene and derivatives thereof, the PH value of the electron conducting polymer is 1-5, and the electron conducting polymer can be self-polymerized at high temperature.
8. The method according to claim 7, wherein the lithium metal composite oxide has a chemical formula (Li 2 O)x-(MαO 2 )y-(NO 3 ) z, N element at least contains one or two of Al, ti, zr and Sn; the chemical formula of the lithium phosphorus compound is (Li 2 O)x-(MαO 2 )y-(PO 4 ) z; the chemical formula of the lithium boron complex compound is (Li 2 O)x-(MαO 2 )y-(BO 3 ) z, M is at least one selected from Ti, ge, la, zr, sr, al, Y, ta, W, nb, mn and yttrium, wherein x is more than or equal to 0.1 and less than or equal to 2.0,0.25, alpha is more than or equal to 4.0,0, y is more than or equal to 2.0,0.1 and z is more than or equal to 4.0.
9. Use of a battery positive electrode material in a positive electrode sheet of a lithium ion battery, characterized in that the battery positive electrode material is prepared by the preparation method according to any one of claims 3-8.
10. A lithium ion battery having the positive electrode sheet of the sodium ion battery of claim 9.
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| CN117543007A (en) * | 2024-01-09 | 2024-02-09 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
| CN117577832A (en) * | 2024-01-16 | 2024-02-20 | 中国第一汽车股份有限公司 | Lithium manganese iron phosphate positive electrode material and preparation method thereof, positive electrode plate and preparation method thereof, lithium ion battery and electric equipment |
| CN117577832B (en) * | 2024-01-16 | 2024-05-14 | 中国第一汽车股份有限公司 | Lithium manganese iron phosphate positive electrode material and preparation method thereof, positive electrode plate and preparation method thereof, lithium ion battery and electric equipment |
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| CN117543007A (en) * | 2024-01-09 | 2024-02-09 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
| CN117543007B (en) * | 2024-01-09 | 2024-03-29 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
| CN117577832A (en) * | 2024-01-16 | 2024-02-20 | 中国第一汽车股份有限公司 | Lithium manganese iron phosphate positive electrode material and preparation method thereof, positive electrode plate and preparation method thereof, lithium ion battery and electric equipment |
| CN117577832B (en) * | 2024-01-16 | 2024-05-14 | 中国第一汽车股份有限公司 | Lithium manganese iron phosphate positive electrode material and preparation method thereof, positive electrode plate and preparation method thereof, lithium ion battery and electric equipment |
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