CN115020685A - Lithium iron manganese phosphate positive electrode material and preparation method and application thereof - Google Patents
Lithium iron manganese phosphate positive electrode material and preparation method and application thereof Download PDFInfo
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- CN115020685A CN115020685A CN202210885550.0A CN202210885550A CN115020685A CN 115020685 A CN115020685 A CN 115020685A CN 202210885550 A CN202210885550 A CN 202210885550A CN 115020685 A CN115020685 A CN 115020685A
- Authority
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- China
- Prior art keywords
- sintering
- source
- lithium
- phosphate
- positive electrode
- Prior art date
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Links
- 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 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 109
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 69
- 238000002156 mixing Methods 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 33
- 239000010405 anode material Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 21
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 21
- 239000004254 Ammonium phosphate Substances 0.000 claims description 18
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 18
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 18
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000005580 one pot reaction Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000007039 two-step reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 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 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 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 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 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 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005253 cladding Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 32
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract 4
- 239000011148 porous material Substances 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000010416 ion conductor Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011570 LiFe 1-x Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium iron manganese phosphate positive electrode material as well as a preparation method and application thereof, wherein the lithium iron manganese phosphate positive electrode material comprises a substrate material and a coating material arranged on the surface of the substrate material, the substrate material has a porous structure, and the chemical formula of the substrate material is LiFe 1‑x‑a Mn x M a PO 4 M is at least one of Ti, Zr and Al elements, 0<x is less than or equal to 0.2, a is less than or equal to 0.01 and less than or equal to 0.05, the electrochemical performance of the cathode material is optimized by doping and increasing the pore structure and coating of the material, and the doped cathode material with high energy density and good rate capability is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium iron manganese phosphate positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries are increasingly widely used in the fields of small portable devices, new energy vehicles, energy storage and the like. Lithium iron phosphate is used as a lithium ion battery cathode material, has excellent safety performance and cycle performance, does not pollute the environment, is considered to be a power lithium ion battery material with great potential, and becomes a hotspot of development and research in recent years, but the lithium iron manganese phosphate cathode material has the technical problems of low energy density and poor rate capability.
Compared with lithium iron phosphate material, LiFe 1-x Mn x PO 4 The cathode material has higher working voltage (3.5-4.1V), which means that the cathode material has higher energy density, but the rate capability of the cathode material is still poor, and Mn in the material is easy to dissolve and is unstable during high-voltage charging, so that the rate capability and the material stability of the cathode material need to be further improved.
CN113636532A discloses a preparation method of a modified lithium iron manganese phosphate cathode material, which comprises the following steps: a. carrying out nanocrystallization on the micron-sized lithium manganese iron phosphate and a dispersing agent to obtain nanoscale lithium manganese iron phosphate slurry; carrying out nanocrystallization on the micron-sized solid electrolyte to obtain nanoscale solid electrolyte slurry; b. drying the lithium iron manganese phosphate slurry and the solid electrolyte slurry, and uniformly mixing to obtain a composite material; c. calcining the composite material in an inert atmosphere to obtain a modified lithium iron manganese phosphate anode material; wherein the dispersant is one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol, and the addition amount of the dispersant is 1 to 5 weight percent of the manganese lithium iron phosphate; the content of the solid electrolyte in the modified lithium iron manganese phosphate anode material is 0.3 wt% -3 wt%.
CN112864368A discloses a preparation method of a composite coated modified lithium manganese iron phosphate anode material, which utilizes the mutual promotion effect between the hydrolysis of a silicon source and the polymerization process of dopamine to carry out the composite coating modification of the lithium manganese iron phosphate at room temperature, and then the composite coating modification is calcined to obtain SiO 2 And nitrogen-doped carbon co-coated lithium manganese iron phosphate.
The lithium iron manganese phosphate cathode material has the problems of poor rate capability and poor stability, so that the development of the lithium iron manganese phosphate cathode material with good rate capability and good stability is necessary.
Disclosure of Invention
The invention aims to provide a lithium iron manganese phosphate positive electrode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium iron manganese phosphate anode material, which comprises a base material and a coating material arranged on the surface of the base material, wherein the base material has a porous structure, and the chemical formula of the base material is LiFe 1-x-a Mn x M a PO 4 M is at least one of Ti, Zr and Al elements, 0<x ≦ 0.2, for example: 0.01, 0.05, 0.1, 0.15, or 0.2, etc., 0.01. ltoreq. a.ltoreq.0.05, for example: 0.01, 0.02, 0.03, 0.04, 0.05, etc.
In the lithium iron manganese phosphate anode material, the existence of manganese can improve the energy density of the material, and the doping of other elements is carried out on the matrix material, so that defects are generated in the crystal, and the defects are favorable for Li + Due to different charge valence states, charge difference is generated, and a cation vacancy is formed through a charge compensation mechanism, so that the conductivity of the material is improved, and the rate capability of the material is improved. For the matrix material with the porous structure, the electrolyte can enter the internal holes, so that the migration rate of lithium ions can be effectively improved, and the rate performance is improved.
Preferably, the coating material comprises lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 )。
In the lithium iron manganese phosphate anode material, Li 3 V 2 (PO 4 ) 3 The coating of the material prevents the matrix material from directly contacting with the electrolyte, reduces the dissolution of Mn, is favorable for improving the cycle performance of the material, and simultaneously Li 3 V 2 (PO 4 ) 3 Is a fast ion conductor material which increases Li on the surface of the anode material + The transmission channel improves the ionic conductivity of the material, and compared with other non-electrochemically active fast ion conductors, Li 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring the capacity loss of the material due to coating.
Preferably, the mass fraction of the matrix material is 90-98% based on 100% of the mass of the lithium iron manganese phosphate cathode material, for example: 90%, 92%, 94%, 96%, 98%, etc.
Preferably, the mass fraction of the coating layer material is 2-10%, for example: 2%, 4%, 6%, 8%, 10%, etc.
In a second aspect, the invention provides a preparation method of the lithium iron manganese phosphate positive electrode material in the first aspect, and the preparation method includes the following steps:
(1) mixing an iron source, a manganese source and a doped metal source with a solvent, adding a first phosphorus source and an organic carbon source, carrying out one-step reaction to obtain a first precipitate, and carrying out one-step sintering treatment on the obtained precipitate to obtain an iron phosphate precursor material with a porous structure;
(2) mixing the iron phosphate precursor material obtained in the step (1) with a lithium source, and performing two-step sintering treatment to obtain a base material;
(3) mixing a vanadium source, a lithium source and a solvent, adding the base material obtained in the step (2) to obtain a suspension, adding a second phosphorus source to obtain a second precipitate through a two-step reaction, and sintering the second precipitate in three steps to obtain the lithium iron manganese phosphate anode material.
In the preparation process of the lithium iron manganese phosphate cathode material, an organic carbon source is cracked and oxidized by oxygen in the sintering process to generate carbon dioxide and water, and the carbon dioxide and the water form a loose porous structure, so that an electrolyte can enter internal holes, the migration rate of lithium ions can be effectively improved, and the rate capability can be improved.
Preferably, the iron source of step (1) comprises at least one of ferrous sulfate, ferrous chloride, ferric nitrate or ferrous oxalate.
Preferably, the source of manganese comprises at least one of manganous sulfate, manganous chloride or manganous nitrate.
Preferably, the source of doping metal comprises at least one of titanium sulfate, titanium chloride, titanium nitrate, zirconium sulfate, zirconium chloride, zirconium nitrate, aluminum sulfate, aluminum chloride or aluminum nitrate.
Preferably, the first phosphorus source comprises ammonium phosphate and/or ammonium dihydrogen phosphate.
Preferably, the organic carbon source comprises at least one of glucose, sucrose, starch, maltose or polyethylene glycol.
Preferably, the mass of the organic carbon source is 15 to 35% based on 100% of the mass of the iron phosphate precursor material, for example: 15%, 18%, 20%, 25%, 30%, 35%, etc.
Preferably, the temperature of the one-step reaction in the step (1) is 20-50 ℃, for example: 20 ℃, 25 ℃, 30 ℃, 40 ℃ or 50 ℃ and the like.
Preferably, the time of the one-step reaction is 3-8 h, for example: 3h, 4h, 5h, 6h, 7h or 8h and the like.
Preferably, after the one-step reaction, the obtained solid is subjected to suction filtration, washing, water washing and drying.
Preferably, the temperature of the one-step sintering treatment is 500-750 ℃, for example: 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C or 750 deg.C.
Preferably, the time of the one-step sintering treatment is 2-5 h, for example: 2h, 2.5h, 3h, 4h or 5h and the like.
Preferably, the two-step sintering process of step (2) includes a first sintering and a second sintering.
Preferably, the temperature of the primary sintering is 200-300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃ or the like.
Preferably, the time of the primary sintering is 3-5 h, for example: 3h, 3.5h, 4h, 4.5h or 5h and the like.
Preferably, the temperature of the secondary sintering is 600-800 ℃, for example: 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C, etc.
Preferably, the time of the secondary sintering is 8-15 h, for example: 8h, 9h, 10h, 12h or 15h and the like.
Preferably, the vanadium source of step (2) comprises ammonium metavanadate and/or vanadium pentoxide.
Preferably, the second phosphorus source comprises ammonium phosphate and/or ammonium dihydrogen phosphate.
Preferably, the temperature of the two-step reaction is 20-50 ℃, for example: 20 ℃, 25 ℃, 30 ℃, 40 ℃ or 50 ℃ and the like.
Preferably, the time of the two-step reaction is 3-8 h, for example: 3h, 4h, 5h, 6h, 7h or 8h and the like.
Preferably, after the two-step reaction, the obtained solid is subjected to suction filtration, washing, water washing and drying.
Preferably, the atmosphere of the three-step sintering treatment is an inert atmosphere.
Preferably, the inert atmosphere comprises at least one of nitrogen, helium or argon.
Preferably, the three-step sintering process includes three times of sintering and four times of sintering.
Preferably, the temperature of the third sintering is 200-300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃ or the like.
Preferably, the time of the third sintering is 3-5 h, for example: 3h, 3.5h, 4h, 4.5h or 5h and the like.
Preferably, the temperature of the four times of sintering is 600-800 ℃, for example: 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C, etc.
Preferably, the time of the four times of sintering is 8-15 h, for example: 8h, 9h, 10h, 12h or 15h and the like.
In a third aspect, the present invention provides a positive electrode plate, which is characterized in that the positive electrode plate includes the lithium iron manganese phosphate positive electrode material according to the first aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the lithium iron manganese phosphate anode material, the existence of manganese can improve the energy density of the material, and the doping of other elements is carried out on the matrix material, so that defects are generated in the crystal, and the defects are favorable for Li + Due to different charge valence states, charge difference is generated, and cation vacancies are formed through a charge compensation mechanism, so that the conductivity of the material is improved, and the rate capability of the material is improved. Meanwhile, the organic carbon source is cracked and oxidized by oxygen in the heat preservation process to generate carbon dioxide and water to form a loose porous structure, so that the electrolyte can enter the internal holes, the migration rate of lithium ions can be effectively improved, and the rate performance is improved. And Li 3 V 2 (PO 4 ) 3 The coating of the material prevents the matrix material from directly contacting with the electrolyte, reduces the dissolution of Mn, is beneficial to improving the cycle performance of the material, and simultaneously Li 3 V 2 (PO 4 ) 3 Is a fast ion conductor material which increases Li on the surface of the anode material + The transmission channel improves the ionic conductivity of the material, and compared with other non-electrochemically active fast ion conductors, Li 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring the capacity loss of materials due to coating.
(2) The first discharge specific capacity of the battery made of the lithium iron manganese phosphate cathode material can reach more than 151mAh/g at 5C multiplying power, and the capacity retention rate can reach more than 89% after the battery is cycled for 2000 times at 3C multiplying power.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to a molar ratio of Fe: mn: ti ═ 0.86: 0.1: 0.04 uniformly mixing ferrous sulfate, manganese nitrate and titanium chloride in deionized water, adding ammonium phosphate and glucose (the mass of the glucose is 20% of the mass of the precursor material) while stirring, reacting for 6 hours at 35 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, and then carrying out heat preservation on the dried precipitate sample at 650 ℃ for 3 hours to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 250 ℃ for 4h, and sintering at 700 ℃ for 10h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the mol ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 6 hours at 30 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 4 hours at 250 ℃ in an inert atmosphere, and then sintering for 12 hours at 700 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 95%, and the mass ratio of a coating layer material is 5%.
Example 2
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to the mol ratio of Fe: mn: ti ═ 0.85: 0.11: 0.04 uniformly mixing ferrous sulfate, manganese nitrate and titanium chloride in deionized water, adding ammonium phosphate and glucose (the mass of the glucose is 25% of the mass of the precursor material) while stirring, reacting for 6 hours at 40 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 95 ℃ for vacuum drying for 28 hours, and then preserving the temperature of a dried precipitate sample at 600 ℃ for 3 hours to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 280 ℃ for 4 hours, and sintering at 720 ℃ for 10 hours to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the mol ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 6 hours at 30 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 95 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 4 hours at 280 ℃ in an inert atmosphere, and then sintering for 12 hours at 720 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 94%, and the mass ratio of a coating layer material is 6%.
Example 3
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to a molar ratio of Fe: mn: ti ═ 0.79: 0.20: 0.01 uniformly mixing ferrous sulfate, manganese nitrate and titanium chloride in deionized water, adding ammonium phosphate and sucrose (the mass of sucrose is 35% of the mass of the precursor material) while stirring, reacting for 3h at 50 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25h, and then carrying out heat preservation on the dried precipitate sample at 500 ℃ for 5h to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 200 ℃ for 5h, and sintering at 600 ℃ for 15h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the mol ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding the ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on a product until the pH value of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 5 hours at 200 ℃ in an inert atmosphere, and sintering for 15 hours at 600 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 90%, and the mass ratio of a coating layer material is 10%.
Example 4
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to a molar ratio of Fe: mn: zr is 0.90: 0.05: 0.05 uniformly mixing ferrous sulfate, manganese nitrate and zirconium chloride in deionized water, adding ammonium phosphate and sucrose (the mass of sucrose is 15% of the mass of the precursor material) while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, and then carrying out heat preservation on the dried precipitate sample at 550 ℃ for 5 hours to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 220 ℃ for 4.5h, and sintering at 650 ℃ for 12h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the mol ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 5 hours at 200 ℃ in an inert atmosphere, and then sintering for 12 hours at 650 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 92%, and the mass ratio of a coating layer material is 8%.
Example 5
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to a molar ratio of Fe: mn: zr is 0.82: 0.15: 0.03 uniformly mixing ferrous sulfate, manganese nitrate and zirconium chloride in deionized water, adding ammonium phosphate and starch (the mass of the starch is 18 percent of the mass of the precursor material) while stirring, reacting for 7 hours at 25 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, and then carrying out heat preservation on the dried precipitate sample at 700 ℃ for 2.5 hours to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 250 ℃ for 4.h, and sintering at 750 ℃ for 12h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the mol ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 4 hours at 250 ℃ in an inert atmosphere, and sintering for 10 hours at 750 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 92%, and the mass ratio of the coating layer material is 8%.
Example 6
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to a molar ratio of Fe: mn: al 0.82: 0.16: 0.02 uniformly mixing ferrous sulfate, manganese nitrate and aluminum chloride in deionized water, adding ammonium phosphate and maltose (the mass of maltose is 20% of the mass of the precursor material) while stirring, reacting for 7h at 25 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25h, and then carrying out heat preservation on the dried precipitate sample at 750 ℃ for 2.5h to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 250 ℃ for 4.h, and sintering at 750 ℃ for 12h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the molar ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 4 hours at 300 ℃ in an inert atmosphere, and then sintering for 10 hours at 800 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 98%, and the mass ratio of a coating layer material is 2%.
Example 7
The embodiment provides a lithium iron manganese phosphate anode material, and a preparation method of the lithium iron manganese phosphate anode material comprises the following steps:
(1) according to the mol ratio of Fe: mn: al ═ 0.75: 0.20: 0.05 uniformly mixing ferrous sulfate, manganese nitrate and aluminum chloride in deionized water, adding ammonium phosphate and polyethylene glycol (the mass of the polyethylene glycol is 35% of the mass of the precursor material) while stirring, reacting for 7 hours at 25 ℃, then carrying out suction filtration and washing on the product until the pH of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, and then carrying out heat preservation on the dried precipitate sample at 650 ℃ for 2.5 hours to obtain a loose and porous iron phosphate precursor material;
(2) mixing the iron phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 280 ℃ for 4.h, and sintering at 700 ℃ for 12h to obtain a base material;
(3) uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing the ammonium metavanadate and the lithium carbonate according to the mol ratio of 4:3, adding the base material obtained in the step (2) into a mixed solution, stirring to form a uniform suspension, then adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, then carrying out suction filtration and washing on a product until the pH of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, then transferring the dried precipitate to an atmosphere furnace, sintering for 4 hours at 280 ℃ in an inert atmosphere, and sintering for 10 hours at 700 ℃ to obtain the cathode material, wherein the mass ratio of the base material in the cathode material is 93%, and the mass ratio of a coating layer material is 7%.
Comparative example 1
This comparative example differs from example 1 only in that no dopant metal source was added, and the other conditions and parameters were exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that no organic carbon source was added and other conditions and parameters were exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that no coating layer is added, and the other conditions and parameters are exactly the same as those of example 1.
And (3) performance testing:
1. preparation of lithium Secondary Battery
The positive electrode materials, the conductive agent (Super PTM), and the polyvinylidene fluoride (PVDF) binder obtained in examples 1 to 7 and comparative examples 1 to 3 were mixed at a ratio of 90: 5: 5 in a weight ratio of N-methylpyrrolidone (NMP) solvent, and applying the mixture on an aluminum foil, and drying the resultant, followed by rolling to prepare a positive electrode;
respectively mixing artificial graphite, a conductive agent (Super PTM), carboxymethyl cellulose and styrene butadiene rubber in a weight ratio of 92: 4: 2: 2 to NMP to prepare a negative electrode mixture, coating the negative electrode mixture on a copper foil, drying the resultant, and then rolling to prepare a negative electrode;
an electrode assembly was prepared by placing a porous polyethylene separator between the positive and negative electrodes prepared above, the electrode assembly was placed in a case, and then an electrolyte was injected into the case to prepare a lithium secondary battery. An electrolyte was prepared by dissolving 1.15M lithium hexafluorophosphate in an organic solvent formed of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) (mixed volume ratio of EC/DMC/EMC: 3/4/3).
2. Testing of Positive Material Properties
Charging the lithium secondary battery with 1C up to 4.2V/0.05C under a constant current/constant voltage (CC/CV) condition at 25 ℃, and then discharging to 3.0V with 5C under a Constant Current (CC) condition, calculating a specific discharge capacity;
the lithium secondary battery was charged up to 4.2V/0.05C with 3C under constant current/constant voltage (CC/CV) conditions at 25 ℃, and then discharged to 3.0V with 3C under Constant Current (CC) conditions. This was used as one cycle and the experiment was repeated for 2000 cycles. The capacity retention rate at the 2000 th cycle during charging and discharging was measured.
The test results are shown in Table 1
TABLE 1
As can be seen from table 1, in examples 1 to 7, the first specific discharge capacity of the battery made of the lithium iron manganese phosphate positive electrode material of the present invention at a 5C rate can reach 151mAh/g or more, and the capacity retention rate can reach 89% or more after the battery is cycled for 2000 times at a 3C rate.
In the preparation process of the lithium manganese iron phosphate cathode material, the performance of the lithium manganese iron phosphate cathode material is influenced by the addition amount of the organic carbon source, the weight of the organic carbon source is controlled to be 15-35% of the weight of the finally prepared iron phosphate precursor material, the performance of the prepared lithium manganese iron phosphate cathode material is good, if the addition amount of the organic carbon source is too low, an effective conductive network is difficult to form, and the improvement effect of C on the material is reduced; if the addition amount of the organic carbon source is too large, the problems of low compacted density and low gram capacity of the prepared cathode material can be caused.
Compared with the comparative example 1, the invention dopes transition metal in the lithium iron manganese phosphate anode material, and the doping generates defects in the crystal, and the defects are beneficial to Li + Due to different charge valence states, charge difference is generated, and cation vacancies are formed through a charge compensation mechanism, so that the conductivity of the material is improved, and the rate capability of the material is improved.
Compared with the comparative example 2, the embodiment 1 can obtain that the electrolyte can enter the internal holes because the organic carbon source is cracked and oxidized by oxygen in the heat preservation process to generate carbon dioxide and water to form a loose porous structure, so that the migration rate of lithium ions can be effectively improved, and the rate performance can be improved.
From example 1 and comparative example 3, Li 3 V 2 (PO 4 ) 3 The coating of the material prevents the matrix material from directly contacting with the electrolyte, reduces the dissolution of Mn, is beneficial to improving the cycle performance of the material, and simultaneously Li 3 V 2 (PO 4 ) 3 Is a fast ion conductor material which increases Li on the surface of the anode material + The transmission channel improves the ionic conductivity of the material, and compared with other non-electrochemically active fast ion conductors, Li 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring the capacity loss of materials due to coating.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. The lithium iron manganese phosphate anode material is characterized by comprising a base material and a coating layer material arranged on the surface of the base material, wherein the base material is porousThe structure is characterized in that the chemical formula of the base material is LiFe 1-x-a Mn x M a PO 4 M is at least one of Ti, Zr and Al elements, 0<x≤0.2，0.01≤a≤0.05。
2. The lithium iron manganese phosphate positive electrode material of claim 1, wherein the cladding material comprises lithium vanadium phosphate.
3. The lithium iron manganese phosphate positive electrode material according to claim 1 or 2, wherein the matrix material is 90 to 98% by mass based on 100% by mass of the lithium iron manganese phosphate positive electrode material;
preferably, the mass fraction of the coating layer material is 2-10%.
4. A method for preparing the lithium iron manganese phosphate positive electrode material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing an iron source, a manganese source and a doped metal source with a solvent, adding a first phosphorus source and an organic carbon source, carrying out one-step reaction to obtain a first precipitate, and carrying out one-step sintering treatment on the obtained precipitate to obtain an iron phosphate precursor material with a porous structure;
(2) mixing the iron phosphate precursor material obtained in the step (1) with a lithium source, and performing two-step sintering treatment to obtain a base material;
(3) mixing a vanadium source, a lithium source and a solvent, adding the base material obtained in the step (2) to obtain a suspension, adding a second phosphorus source to obtain a second precipitate through a two-step reaction, and sintering the second precipitate in three steps to obtain the lithium iron manganese phosphate anode material.
5. The method of claim 4, wherein the iron source of step (1) comprises at least one of ferrous sulfate, ferrous chloride, ferric nitrate, or ferrous oxalate;
preferably, the manganese source comprises at least one of manganous sulfate, manganous chloride, or manganous nitrate;
preferably, the source of doping metal comprises at least one of titanium sulfate, titanium chloride, titanium nitrate, zirconium sulfate, zirconium chloride, zirconium nitrate, aluminum sulfate, aluminum chloride, or aluminum nitrate;
preferably, the first phosphorus source comprises ammonium phosphate and/or ammonium dihydrogen phosphate;
preferably, the organic carbon source comprises at least one of glucose, sucrose, starch, maltose or polyethylene glycol;
preferably, the mass of the organic carbon source is 15-35% based on 100% of the mass of the iron phosphate precursor material.
6. The preparation method according to claim 4 or 5, wherein the temperature of the one-step reaction in the step (1) is 20-50 ℃;
preferably, the one-step reaction time is 3-8 h;
preferably, after the one-step reaction, carrying out suction filtration, washing, water washing and drying on the obtained solid;
preferably, the temperature of the one-step sintering treatment is 500-750 ℃;
preferably, the time of the one-step sintering treatment is 2-5 h.
7. The production method according to any one of claims 4 to 6, wherein the two-step sintering treatment of step (2) includes primary sintering and secondary sintering;
preferably, the temperature of the primary sintering is 200-300 ℃;
preferably, the time for primary sintering is 3-5 h;
preferably, the temperature of the secondary sintering is 600-800 ℃;
preferably, the time of the secondary sintering is 8-15 h.
8. The production method according to any one of claims 4 to 7, wherein the vanadium source of step (2) comprises ammonium metavanadate and/or vanadium pentoxide;
preferably, the second phosphorus source comprises ammonium phosphate and/or ammonium dihydrogen phosphate;
preferably, the temperature of the two-step reaction is 20-50 ℃;
preferably, the time of the two-step reaction is 3-8 h;
preferably, after the two-step reaction, carrying out suction filtration, washing, water washing and drying on the obtained solid;
preferably, the atmosphere of the three-step sintering treatment is an inert atmosphere;
preferably, the inert atmosphere comprises at least one of nitrogen, helium or argon;
preferably, the three-step sintering treatment comprises three times of sintering and four times of sintering;
preferably, the temperature of the third sintering is 200-300 ℃;
preferably, the time for the third sintering is 3-5 h;
preferably, the temperature of the four times of sintering is 600-800 ℃;
preferably, the time for the four times of sintering is 8-15 h.
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises the lithium iron manganese phosphate positive electrode material according to any one of claims 1 to 3.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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