WO2022057920A1 - 正极材料、正极片及电池 - Google Patents
正极材料、正极片及电池 Download PDFInfo
- Publication number
- WO2022057920A1 WO2022057920A1 PCT/CN2021/119310 CN2021119310W WO2022057920A1 WO 2022057920 A1 WO2022057920 A1 WO 2022057920A1 CN 2021119310 W CN2021119310 W CN 2021119310W WO 2022057920 A1 WO2022057920 A1 WO 2022057920A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium iron
- positive electrode
- phosphate material
- manganese phosphate
- iron manganese
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 207
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011572 manganese Substances 0.000 claims abstract description 55
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 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 119
- 239000002245 particle Substances 0.000 claims description 72
- 239000011164 primary particle Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 7
- PVIWTECCOFKIAF-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Fe+2].[Fe+2].[Mn+2].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Fe+2].[Mn+2].[Li+] PVIWTECCOFKIAF-UHFFFAOYSA-K 0.000 claims description 6
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract 9
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 abstract 9
- 239000011267 electrode slurry Substances 0.000 description 21
- 238000005056 compaction Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 9
- 239000011163 secondary particle Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- BECVLEVEVXAFSH-UHFFFAOYSA-K manganese(3+);phosphate Chemical class [Mn+3].[O-]P([O-])([O-])=O BECVLEVEVXAFSH-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 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
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/364—Composites as mixtures
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
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- H01M10/052—Li-accumulators
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of batteries, in particular to a positive electrode material, a positive electrode sheet and a battery.
- the cathode material of lithium-ion batteries is critical to the performance of the battery.
- the positive electrode materials commonly used in power batteries include ternary materials, lithium iron phosphate materials, and lithium manganese iron phosphate materials.
- lithium manganese iron phosphate (LMFP for short) has higher safety and cyclability than ternary materials, and its potential is much higher than that of phosphoric acid.
- the potential of lithium iron (the potential of lithium iron phosphate is 3.4V) is expected to improve the energy density of the battery. Therefore, the lithium manganese iron phosphate material with higher safety and higher energy density has gradually become the mainstream cathode material for power batteries.
- the common product forms of LMFP on the market are mainly single-crystal-like and agglomerate.
- the single-crystal-like material is composed of one or a few (no more than 5) primary particles, with very few internal grain boundaries; agglomerates
- the material is a secondary particle material formed by agglomeration of many primary particles, and there are many internal grain boundaries.
- the primary particles of single-crystal LMFP-like materials are relatively large, so that the degree of manganese dissolution of such materials during the battery cycle is low, but their capacity is low under the same metal ratio; while the primary particles of agglomerates are small and the specific surface area is small.
- the present application provides a positive electrode material, a positive electrode sheet and a battery, wherein, by designing the particle size of a variety of LMFP materials with different particle sizes in the positive electrode material, the morphology of the LMFP materials with different particle sizes, and the Mn/Fe molar ratio The design can optimize the electrochemical performance of the battery under the condition that the positive electrode sheet made of the positive electrode material has a suitable compaction density.
- the application provides a positive electrode material
- the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth iron manganese phosphate material.
- Lithium material and fifth lithium iron manganese phosphate material wherein, the first lithium iron manganese phosphate material is agglomerates, and the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, so The second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are respectively agglomerates and/or quasi-single crystals, and satisfy the following particle size relationship:
- the D 50 1 to D 50 5 represent the values of the particle sizes D50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material in sequence, and the unit is ⁇ m; the value of a The range is 0.35-0.5, the value range of the b is 0.2-0.27, the value range of the c is 0.17-0.18, and the value range of the d is 0.15-0.16;
- the molar ratio of manganese to iron of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, and the fourth lithium iron manganese iron phosphate material increases sequentially, and the fifth lithium iron manganese iron phosphate material increases sequentially.
- the molar ratio of manganese to iron of the material is greater than that of the third lithium iron manganese phosphate material.
- the present application provides a positive electrode slurry, the positive electrode slurry includes the positive electrode material described in the first aspect of the present application, a conductive agent and a solvent.
- the present application provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, the positive electrode material layer includes the positive electrode material described in the first aspect of the present application, Alternatively, the positive electrode slurry described in the second aspect of the present application is used to coat the current collector.
- the present application provides a battery including the positive electrode sheet described in the third aspect of the present application.
- the beneficial effects of the present application include: when the five kinds of lithium manganese iron phosphate materials contained in the positive electrode material provided by the present application meet the above-mentioned specific D 50 particle size relationship, the above-mentioned specific morphology requirements and specific Mn/Fe molar ratio requirements, they are composed of
- the positive electrode sheet made of the positive electrode material has a higher compaction density, and the battery with the positive electrode sheet simultaneously has excellent electrical properties such as higher capacity, voltage platform, cycle stability, and lower amount of dissolved manganese.
- an embodiment of the present application provides a positive electrode material, and the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth manganese iron phosphate material.
- a lithium iron material and a fifth lithium iron manganese phosphate material wherein, the first lithium iron manganese phosphate material is agglomerates, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, and the second manganese iron phosphate material is quasi-single crystal.
- the lithium iron material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals, respectively, and satisfy the following particle size relationship:
- D 50 1 to D 50 5 represent the values of particle size D 50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material in sequence, and the unit is ⁇ m; the value range of a is 0.35 -0.5, the value range of b is 0.2-0.27, the value range of c is 0.17-0.18, and the value range of d is 0.15-0.16;
- the molar ratio of manganese to iron of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, and the fourth lithium iron manganese iron phosphate material increases sequentially, and the fifth lithium iron manganese iron phosphate material increases sequentially.
- the molar ratio of manganese to iron of the material is greater than that of the third lithium iron manganese phosphate material.
- the above-mentioned D 50 1 to D 50 5 can be regarded as the particle size of the respective secondary particles in order (if the LMFP-based single crystal material consists of one primary particle, it can also be regarded as a "secondary particle") .
- LMFP materials with different morphologies, different particle size D 50 values, and different Mn/Fe molar ratios affect the rate performance of the battery, the cycle stability of the battery, and the amount of dissolved Mn.
- the first lithium manganese iron phosphate material in the form of agglomerates has many grain boundaries, and the energy barrier to be overcome by the diffusion of lithium ions in it is large, but the particle size of the primary particles that make it up is small, and the diffusion path of lithium ions in it is short. , the Mn/Fe molar ratio is the smallest, the rate performance is better, and it can also help to reduce the degree of high soluble Mn caused by the large specific surface area of the material.
- the fourth and fifth lithium manganese iron phosphate materials in the form of single crystals have fewer grain boundaries and small diffusion energy barriers, but their primary particle size is large, the diffusion path of lithium ions in them is long, and the Mn/Fe molar ratio is relatively high.
- the charge and discharge capabilities of the above five kinds of lithium iron manganese phosphate materials can be basically the same, and the structures are relatively stable.
- the battery made of the positive electrode material can have good rate performance, high capacity, high discharge platform, high cycle stability, low dissolved manganese and other excellent properties.
- the positive electrode sheet made from the above-mentioned positive electrode material can also have better compaction density. If the above-mentioned a, b, c, and d are not within the above ranges, then the five kinds of lithium manganese iron phosphate materials cannot be well differentiated in particle size, so it is impossible to rely on the multi-level difference between LMFP materials of different particle size grades. Filling to increase the compaction density of the pole pieces made from them.
- the value range of the a is 0.41 ⁇ a ⁇ 0.45, and the value range of the b is 0.21 ⁇ b ⁇ 0.23.
- the a is 0.41, the b is 0.23, the c is 0.18, and the d is 0.16.
- the D 50 1 of the first lithium iron manganese phosphate material is too small, the compaction density of the positive electrode sheet will still be low even under the combination of the above-mentioned various particles of different sizes;
- the D 50 1 of the lithium material is too small, and its primary particle size is lower, and the specific surface area of the first lithium iron manganese phosphate material will increase, thereby increasing the side reaction between it and the electrolyte, and the first lithium iron manganese phosphate material will increase.
- the structural stability of the material deteriorated during cycling and the amount of dissolved Mn increased.
- the compaction density of the positive electrode sheet will also be reduced to a certain extent; Fourth, the particle size of the fifth lithium iron manganese phosphate material will also be large, which will lengthen the diffusion path of lithium ions in these two materials, thereby reducing the rate performance of the battery.
- the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals respectively" can be understood as the second lithium iron manganese phosphate material is aggregates or quasi-single crystals or both. It contains agglomerates and quasi-single crystals.
- the third lithium iron manganese phosphate material is agglomerates or quasi-single crystals or contains both agglomerates and quasi-single crystals.
- the Mn/Fe molar ratios of the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, and the fourth lithium iron manganese phosphate material increase sequentially, and the fourth and fifth The Mn/Fe molar ratio of the lithium manganese iron phosphate material is sequentially larger than the Mn/Fe molar ratio of the third lithium iron manganese phosphate material, and the Mn/Fe molar ratio of the third lithium iron manganese phosphate material is greater than that of the second lithium iron manganese phosphate material.
- the Mn/Fe molar ratio of the second lithium manganese iron phosphate material is greater than the Mn/Fe molar ratio of the first lithium manganese iron phosphate material.
- the Mn/Fe molar ratio of the fifth lithium iron manganese phosphate material may be equal to or different from the Mn/Fe molar ratio of the fourth lithium iron manganese phosphate material.
- the Mn/Fe molar ratio of the first lithium iron manganese phosphate material is 1-1.25.
- the Mn/Fe molar ratio of the second lithium iron manganese phosphate material is 1.5-2.33.
- the Mn/Fe molar ratio of the third lithium iron manganese phosphate material is 2.33-4.
- the Mn/Fe molar ratios of the fourth lithium iron manganese phosphate material and the fifth lithium manganese iron phosphate material are respectively 4-9.
- the Mn/Fe molar ratios of the five LMFP materials are in these ranges, and the above five kinds of manganese phosphates can be The consistency of charge and discharge levels of iron-lithium materials is higher, and the structural stability is higher.
- the median diameter of the primary particles of the agglomerates is in the range of 100 nm-500 nm. That is, the median diameter of the primary particles of the first lithium iron manganese phosphate material is in the range of 100nm-500nm, and the median diameter of the primary particles of the second lithium iron manganese phosphate material in the form of agglomerates is in the range of 100nm-500nm range, the median particle diameter of the primary particles of the third lithium iron manganese phosphate material in the form of agglomerates is in the range of 100 nm-500 nm.
- the agglomerates in the above-mentioned median particle size range can avoid the increase in the number of primary particles constituting the secondary particles of the LMFP material, resulting in an increase in the specific surface area of the secondary particles, thereby avoiding an increase in the specific surface area of the secondary particles.
- the area where side reactions occur increases; at the same time, the crushing rate of secondary particles can be reduced in the process of pressing the positive electrode sheet, thereby avoiding the problem of causing new interfaces to appear and deteriorating battery performance.
- the agglomerates in the above-mentioned median particle size range can reduce the diffusion path of lithium ions in the secondary particle material, thereby avoiding the problems that the capacity of the LMFP material is low, the battery impedance increases, and the power performance decreases.
- the median particle size of the agglomerates is in the above range, which can avoid the increase of side reactions with the electrolyte due to the too small primary particles of the agglomerates, thereby avoiding the deterioration of the structural stability of the agglomerates and the increase in the amount of dissolved Mn.
- the diffusion path of lithium ions in the agglomerates can be more suitable, so that the battery rate performance is better.
- the primary particle size of the single crystal-like is in the range of 0.5 ⁇ m-2.5 ⁇ m. In this way, it can avoid that the single-crystal-like primary particles are too large and the diffusion path of lithium ions is lengthened, and the rate performance of the battery is deteriorated.
- the primary particle size of the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may both be in the range of 1.5 ⁇ m-2.5 ⁇ m, and the third phosphoric acid in the form of a single crystal
- the median particle size of the primary particles of the lithium manganese iron material is in the range of 1.0 ⁇ m-1.5 ⁇ m
- the median particle size of the primary particles of the second lithium iron manganese phosphate material in the quasi-single crystal form is in the range of 0.5 ⁇ m-1.0 ⁇ m.
- the particle number ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6).
- the positive electrode sheet made from the above-mentioned positive electrode material can have a higher compaction density (2.55 g/cm 3 or more).
- the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material The particle number ratio is 1:1:2:8:8.
- the positive electrode sheet can have a very high compaction density (eg, about 2.9 g/cm 3 ).
- the particle mass ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be: 100:14:2.5:0.5:0.3.
- the surfaces of the above-mentioned first to fifth lithium iron manganese phosphate materials may all have a carbon coating layer, so that the electrical conductivity of each of the lithium iron manganese phosphate materials can be improved.
- the LMFP materials in the form of agglomerates can be prepared in the following manner:
- the raw materials (manganese source, iron source, phosphorus source, lithium source and carbon source) for synthesizing LMFP are mixed according to a certain mass ratio, and the mixed material is wet-ground with water to grind to a particle size of 40nm- 60nm;
- the sintering process sequentially includes a first heating section, a first constant temperature section, a second heating section, a second constant temperature section and a cooling section; wherein, The first heating section is from room temperature to the first constant temperature (such as 400°C), and the heating time can be 2.5h-3.5h; the constant temperature time of the first constant temperature section is 3.5h-5.5h; the second heating section is The first constant temperature (such as 400 ° C) rises to the second constant temperature (such as 700 ° C), and the heating time can be 2.5h-4.0h; the constant temperature time of the second constant temperature section can be 2.5h-4.5h; The second constant temperature (such as 700°C) is lowered to about 50°C, and the cooling time is 5.5h-7.5h.
- the first constant temperature such as 400° C
- the heating time rises to the second constant temperature (such as 700 ° C)
- the heating time can be 2.5h-4.0h
- the constant temperature time of the second constant temperature section can be 2.5h-4.5h
- the sintered material is subjected to airflow crushing, wherein the pressure of the airflow crushing can be 3MPa-5MPa, and the time can be 2h-3h; then screen and classify to obtain the material with the desired particle size D50.
- the mixing time in the above step (1), may be 0.5h-1.5h, and according to another embodiment of the present application, the mixing time in the above step (1) may be 0.75h-1.2 h.
- ferromanganese phosphate can be selected as the manganese source, iron source and phosphorus source at the same time.
- the lithium source may include, but is not limited to, at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, and lithium acetate.
- the carbon source includes, but is not limited to, at least one of glucose, sucrose, starch, fructose, citric acid, ascorbic acid, and polyethylene glycol.
- a grinding medium with a diameter of 0.6mm-0.8mm may be used to grind the material until the particle size of the material is below 50 ⁇ m, and then a grinding medium with a diameter of 0.1mm-0.3mm may be used for grinding.
- the medium is ground until the particle size of the material is 40nm-60nm;
- the inlet temperature during spray drying can be 150°C-200°C, and according to another embodiment of the present application, the inlet temperature during spray drying is 160°C-180°C .
- the above-mentioned preparation methods of the quasi-single-crystal LMFP material and the LMFP material of the agglomerate form are different in that the first constant temperature and the second constant temperature during sintering are different, and the pressure of airflow crushing is different.
- the first heating section is raised from room temperature to a first constant temperature (such as 450°C), and the heating time can be 2.5h-3.5h; the first constant temperature The constant temperature time of the heating section is 3.5h-5.5h; the second heating section is from the first constant temperature (such as 450°C) to the second constant temperature (eg 750°C), and the heating time can be 2.5h-4.0h; The constant temperature time of the constant temperature section can be 2.5h-4.5h; the cooling section is from the second constant temperature (such as 750°C) to about 50°C, and the cooling time is 6.5h-8.5h.
- airflow crushing can be carried out under the pressure of 5MPa-8MPa for 2h-3h;
- Embodiments of the present application further provide a positive electrode slurry, and the positive electrode slurry includes the above-mentioned positive electrode material.
- the positive electrode slurry also includes a conductive agent, a binder and a solvent.
- the mass ratio of the positive electrode material, the conductive agent and the binder is 100:(0.5-5):(0.5-5).
- the solid content of the positive electrode slurry is 10wt%-80wt%.
- the conductive agent includes at least one of carbon nanotubes, carbon black and graphene, and according to another embodiment of the present application, the conductive agent includes three kinds of carbon nanotubes, carbon black and graphene,
- the three-dimensional conductive agent can make the positive electrode material layer formed from the positive electrode slurry have better conductivity. Further, the mass ratio of carbon nanotubes, carbon black and graphene may be 6:5:2.
- the binder is a conventional choice in the battery field, for example, it can be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), polypropylene
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PVA polyvinyl alcohol
- SBR styrene butadiene rubber
- PAN polyimide
- PAA polyacrylic acid
- CMC sodium carboxymethylcellulose
- alginate sodium alginate
- PVDF can refer to a copolymer obtained by the copolymerization of vinylidene fluoride and an olefin compound containing a polar group
- the polar group includes at least one of a carboxyl group, an epoxy group, a hydroxyl group and a sulfonic acid group. The existence of the group can enhance the peel strength between the positive electrode material layer formed by the positive electrode slurry and the current collector.
- the solvent is a conventional choice in the battery field, for example, N-methylpyrrolidone (NMP) is used.
- NMP N-methylpyrrolidone
- the positive electrode slurry may further contain a dispersant, so as to better improve the dispersibility and stability of the positive electrode slurry.
- the dispersant may be polyvinylpyrrolidone (PVP) or the like.
- the first LMFP material, the second LMFP material and the third LMFP material with larger particle size can be directly added in the form of their powder, which can prevent sedimentation during slurry mixing, and the particle size is relatively small.
- the small fourth LMFP material and the fifth LMFP material can be added either in the form of powder or in the form of slurries, wherein, in addition to organic solvents, the respective slurries can also contain dispersants, such as PVP etc.
- an embodiment of the present application further provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, and the positive electrode material layer includes the above-mentioned positive electrode material Or use the above-mentioned positive electrode slurry to coat the current collector.
- the positive electrode sheet containing the above positive electrode material has a high compaction density.
- the positive electrode material layer also includes a conductive agent and a binder.
- the positive electrode material layer can be formed by coating the above-mentioned positive electrode slurry on the current collector.
- an embodiment of the present application further provides a battery including the above positive electrode sheet.
- the battery also has excellent electrical properties such as higher capacity, lower probability of dissolving manganese, and higher cycle stability.
- the first to fifth LMFP materials that meet the above morphology requirements are respectively recorded as particle 1, particle 2, particle 3, particle 4, and particle 5, and select 5 according to the particle size, quantity, and Mn/Fe molar ratio in Table 1.
- the particles are prepared for subsequent mixing to obtain positive electrode materials corresponding to different embodiments.
- test methods of each item of each LMFP material are as follows:
- the testing method for the particle size of each LMFP material is as follows: the testing equipment is a laser particle size analyzer, and the reference model is Malvern 2000/3000.
- the test method is: disperse each LMFP material in deionized water, ultrasonicate for 10 min, and the particle refractive index is 1.74; perform the test to obtain the particle size D 50 of each LMFP material.
- the method for measuring the number of particles of LMFP materials with different particle sizes is as follows: LMFP materials with different particle sizes are approximately spherical, and the mass of a single sphere is calculated according to the particle size D 50 and bulk density (about 3.6 g/cm 3 ) of each particle. By controlling the feeding quality of LMFP materials with different particle sizes, the number of particles of LMFP materials with different particle sizes is controlled.
- the test method for the median particle size (particle size D 50 ) of the primary particles of each LMFP material is as follows: take a scanning electron microscope (SEM) photograph of each LMFP material at a magnification of 10,000 times, and artificially measure about 300 primary particles. size, and make a number distribution to obtain the median particle size of the primary particles.
- SEM scanning electron microscope
- the Mn/Fe molar ratio of each LMFP material weigh 0.2000g of each LMFP particle, add analytically pure commercially available hydrochloric acid and nitric acid for thermal digestion (wherein, the configuration process of the digestion solution is as follows: take the volume ratio of 1:1 1mL of a mixture of commercially available concentrated hydrochloric acid and water, and then mixed with 3mL of commercially available concentrated nitric acid); then filter with filter paper, and rinse the filter paper with deionized water more than three times to ensure that ions fully enter the filtrate, and then dilute to 100ml, according to GB /T 9723-2007 General rules of chemical reagent flame atomic absorption spectrometry (AAS) test to detect the concentration of Fe and Mn ions, and calculate the Mn/Fe molar ratio.
- AAS chemical reagent flame atomic absorption spectrometry
- Preparation of positive electrode slurry add a certain proportion of organic solvent NMP and binder PVDF into the mixer, and after stirring for 1 hour, add conductive agent (specifically, carbon tube, carbon black with a mass ratio of 0.6:0.5:0.3) , mixing of graphene), stir for 30min, then add particle 1, particle 2 and particle 3 in the form of their respective powders, after stirring for 1.5h, add the PVP-containing NMP slurry of particle 4 and particle 5, stir for 1.5 hours h, after sieving, the positive electrode slurry is obtained.
- the mass ratio of the positive electrode material composed of particles 1-particles 5 to the conductive agent, the binder PVDF, and the organic solvent NMP is 100:2:2:30.
- Preparation of positive electrode sheet The positive electrode slurry corresponding to each example was coated on both sides of the aluminum foil respectively, and after drying, a positive electrode material layer was formed on the aluminum foil to obtain an unpressed positive electrode sheet. into a size of 40*100mm, and then use a large hydraulic tablet machine to perform tablet compression to obtain a positive electrode tablet after tableting.
- the compaction density of the positive electrode sheet can be calculated according to the areal density of the positive electrode sheet and the thickness after pressing, and the results are summarized in Table 2.
- Preparation of the battery First, prepare the positive electrode slurry corresponding to each example into a single-sided positive electrode sheet with an areal density of 2.0 g/dm 2 and a compacted density of 2.65 g/cm 3 , and make each single-sided positive electrode sheet into a 2025 button type battery.
- the positive electrode slurry corresponding to each embodiment was first prepared into a double-sided positive electrode sheet with an areal density of 4.0 g/dm 2 and a compacted density of 2.65 g/cm 3 ; and then provided with an areal density of 2.1 g/dm 2 and a compacted density It is a double-sided negative electrode sheet of 1.60 g/cm 3 ; the diaphragm is made of PP film, and the 053450 full battery is assembled.
- the test method of specific capacity is: charge the button battery corresponding to each embodiment under constant current and constant voltage (CC-CV) at 0.1C until the voltage is 4.3V, and the cut-off current is 0.05C; The discharge capacity after the third cycle was taken and divided by the amount of dressing of the positive electrode material layer on the positive electrode sheet to calculate the specific capacity of the battery.
- CC-CV constant current and constant voltage
- the median voltage refers to the discharge voltage corresponding to half of the discharge capacity in the discharge curve of 1/3C of the battery.
- the test method of the median voltage is as follows: the full battery corresponding to each embodiment is charged at 1/3C with constant current and constant voltage (CC-CV) until the voltage is 4.3V, and the cut-off current is 0.05C; Current constant voltage discharge until the voltage is 2.5V cut-off. Plot the discharge curve of voltage vs capacity and find the median voltage.
- the test method of the rate performance is: at 25°C, the full battery corresponding to each example is first charged to 4.2V with a constant current of 0.2C, and then discharged to 2.5V with a constant current at different rates of 0.2C and 5C respectively, and the 5C is calculated.
- the ratio of the discharge capacity at 0.2C to the discharge capacity at 0.2C, and this ratio is used to measure the rate performance of the battery.
- the test method for the amount of dissolved Mn in the negative electrode is as follows: at 45°C, the full battery corresponding to each example is charged to 4.3V with a constant current of 1C, and then discharged to 2.5V with a constant current of 1C, after 500 charge-discharge cycles. , disassemble the battery, and test the Mn content in the negative electrode material in the negative pole piece; wherein the Mn content is measured by inductively coupled plasma-emission spectrometer (ICP).
- ICP inductively coupled plasma-emission spectrometer
- the compaction density of the positive electrode sheet can be reduced. Above 2.65 g/cm 3 , the highest can reach 2.86 g/cm 3 , and the specific capacity of the battery is basically not significantly reduced, thereby enabling the battery to have a higher energy density.
- the positive electrode materials of the above-mentioned embodiments can also enable the battery to have high mid-value voltage, good rate capability and relatively excellent cycle performance at the same time.
- the rate performance of the battery made from the positive electrode material of each embodiment is better, and the ratio of discharge capacity at 5C to 0.2C is over 84%, up to 91%, which also shows that the battery has better continuous power.
- the amount of dissolved Mn in the negative electrode was low, below 500 ppm.
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Abstract
Description
Claims (9)
- 一种正极材料,其中,所述正极材料包括第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料;其中,所述第一磷酸锰铁锂材料为团聚体,所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料均为类单晶,所述第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶,且满足以下粒径关系:D 50 5<D 50 4<D 50 3<D 50 2<D 50 1,且D 50 2=aD 50 1,D 50 3=bD 50 1,D 50 4=cD 50 1,D 50 5=dD 50 1,5μm≤D 50 1≤15μm;其中,所述D 50 1至D 50 5依次表示所述第一磷酸锰铁锂材料至所述第五磷酸锰铁锂材料的粒径D 50的值,单位均为μm;所述a的取值范围为0.35-0.5,所述b的取值范围为0.2-0.27,所述c的取值范围是0.17-0.18,所述d的取值范围是0.15-0.16;且所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料的锰铁摩尔比值依次增加,所述第五磷酸锰铁锂材料的锰铁摩尔比值大于所述第三磷酸锰铁锂材料。
- 如权利要求1所述的正极材料,其中,所述第一磷酸锰铁锂材料的锰铁摩尔比值在1-1.25的范围,所述第二磷酸锰铁锂材料的锰铁摩尔比值在1.5-2.33的范围,所述第三磷酸锰铁锂材料的锰铁摩尔比值在2.33-4的范围,所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的锰铁摩尔比值均在4-9的范围。
- 如权利要求1或2所述的正极材料,其中,所述a的取值范围为0.41-0.45;所述b的取值范围为0.21-0.23。
- 如权利要求1-3中任一项所述的正极材料,其中,所述a为0.41,所述b为0.23,所述c为0.18,所述d为0.16。
- 如权利要求1-4中任一项所述的正极材料,其中,所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6)。
- 如权利要求1-5中任一项所述的正极材料,其中,所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比为1:1:2:8:8。
- 如权利要求1-6中任一项所述的正极材料,其中,所述正极材料中,所述团聚体的一次颗粒的中值粒径在100nm-500nm的范围。
- 一种正极片,其中,所述正极片包括集流体和设置在所述集流体上的正极材料层, 所述正极材料层包括如权利要求1-7中任一项所述的正极材料。
- 一种电池,其中,所述电池包括如权利要求8所述的正极片。
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JP2023517872A JP2023542507A (ja) | 2020-09-18 | 2021-09-18 | 正極材料、正極板及び電池 |
EP21868742.4A EP4216314A4 (en) | 2020-09-18 | 2021-09-18 | POSITIVE ELECTRODE MATERIAL, POSITIVE ELECTRODE SHEET AND BATTERY |
KR1020237012323A KR20230069158A (ko) | 2020-09-18 | 2021-09-18 | 양극 재료, 양극 시트 및 배터리 |
US18/121,909 US20230238513A1 (en) | 2020-09-18 | 2023-03-15 | Positive electrode material, positive electrode plate and battery |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2014034775A1 (ja) * | 2012-08-31 | 2014-03-06 | 戸田工業株式会社 | 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法、炭素複合化リン酸マンガン鉄リチウム粒子粉末、及び該粒子粉末を用いた非水電解質二次電池 |
CN104577119A (zh) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | 一种锂离子电池正极材料磷酸锰铁锂及其制备方法 |
CN109250698A (zh) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | 一种高振实密度磷酸锰铁锂正极材料及其制备方法和应用 |
CN109962221A (zh) * | 2019-02-20 | 2019-07-02 | 江西星盈科技有限公司 | 复合正极材料及正极片及正极片制备方法及锂离子电池 |
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WO2014034775A1 (ja) * | 2012-08-31 | 2014-03-06 | 戸田工業株式会社 | 炭素複合化リン酸マンガン鉄リチウム粒子粉末の製造方法、炭素複合化リン酸マンガン鉄リチウム粒子粉末、及び該粒子粉末を用いた非水電解質二次電池 |
CN104577119A (zh) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | 一种锂离子电池正极材料磷酸锰铁锂及其制备方法 |
CN109250698A (zh) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | 一种高振实密度磷酸锰铁锂正极材料及其制备方法和应用 |
CN109962221A (zh) * | 2019-02-20 | 2019-07-02 | 江西星盈科技有限公司 | 复合正极材料及正极片及正极片制备方法及锂离子电池 |
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KR20230069158A (ko) | 2023-05-18 |
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