CN115020685B - 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
- Publication number
- CN115020685B CN115020685B CN202210885550.0A CN202210885550A CN115020685B CN 115020685 B CN115020685 B CN 115020685B CN 202210885550 A CN202210885550 A CN 202210885550A CN 115020685 B CN115020685 B CN 115020685B
- Authority
- CN
- China
- Prior art keywords
- sintering
- source
- lithium
- positive electrode
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 78
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 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
- 238000005245 sintering Methods 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 40
- 239000002244 precipitate Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 30
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 23
- 239000005955 Ferric phosphate Substances 0.000 claims description 21
- 229940032958 ferric phosphate Drugs 0.000 claims description 21
- 229910000399 iron(III) phosphate Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- 238000005580 one pot reaction Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 238000007039 two-step reaction Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 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
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 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
- 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
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 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
- 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
- 229910000398 iron phosphate Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000005336 cracking Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 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
- 239000000047 product Substances 0.000 description 15
- 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
- 238000001291 vacuum drying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 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
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000010416 ion conductor Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000000203 mixture Substances 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
- 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
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001354 calcination Methods 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
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-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
- -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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 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
- 239000010406 cathode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage 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
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 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
- 230000035484 reaction time Effects 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
- 238000004513 sizing Methods 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 manganese iron phosphate positive electrode material, a preparation method and application thereof, wherein the lithium manganese iron phosphate positive electrode material comprises a matrix material and a coating layer material arranged on the surface of the matrix material, the matrix material has a porous structure, and the chemical formula of the matrix material is LiFe 1‑x‑a Mn x M a PO 4 M is at least one of Ti, zr and Al elements, 0<The x is less than or equal to 0.2, a is more than or equal to 0.01 and less than or equal to 0.05, and the electrochemical performance of the anode material is optimized by adopting doping and increasing the pore structure and the coating of the material, so that the doped anode material with high energy density and good multiplying power performance is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium iron manganese phosphate anode material, a preparation method and application thereof.
Background
Lithium ion batteries are increasingly used in the fields of small portable equipment, new energy automobiles, energy storage and the like. The lithium iron phosphate serving as a lithium ion battery anode material has excellent safety performance and cycle performance, is pollution-free to the environment, is considered as a power lithium ion battery material with great potential, and becomes a hot point for development and research in recent years, but the lithium iron manganese phosphate anode material has the technical problems of low energy density and poor multiplying power performance.
LiFe, compared to lithium iron phosphate materials 1-x Mn x PO 4 The positive electrode material has higher working voltage (3.5-4.1V), which means that it has higher energy density, but the rate performance of the positive electrode material is still poor, mn in the material is easy to dissolve and unstable when charged at high voltage, so that the rate performance and the material stability of the positive electrode material need to be further improved.
CN113636532a discloses a preparation method of a modified lithium iron manganese phosphate anode material, which comprises the following steps: a. nano-sizing the micron-sized lithium iron manganese phosphate and the dispersant to obtain nano-sized lithium iron manganese phosphate slurry; nanocrystallizing the micron-sized solid electrolyte to obtain a 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 manganese iron phosphate anode material; wherein the dispersing agent is one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol, and the adding amount of the dispersing agent is 1-5 wt% of lithium manganese iron phosphate; the content of the solid electrolyte in the modified lithium iron manganese phosphate anode material is 0.3-3 wt%.
CN112864368A discloses a preparation method of a composite coated modified lithium iron manganese phosphate anode material, which utilizes the interaction between the hydrolysis of a silicon source and the polymerization process of dopamine to carry out composite coating modification of lithium iron manganese phosphate at room temperature, and then the SiO is obtained by calcining 2 And nitrogen-doped carbon co-coated lithium manganese iron phosphate.
The lithium iron manganese phosphate positive electrode material has the problem of poor rate performance and stability, so that the development of the lithium iron manganese phosphate positive electrode material with good rate performance and good stability is necessary.
Disclosure of Invention
The invention aims to provide a lithium iron manganese phosphate positive electrode material, a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium iron manganese phosphate positive electrode material, which includes a base material and a coating layer material disposed 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,0<x.ltoreq.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 meanwhile, the matrix material is doped with other elements, so that defects are generated in the crystal, and the defects are beneficial to Li + And because of different charge valence states, a 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. For the porous matrix material, electrolyte can enter the internal holes, so that the migration rate of lithium ions can be effectively improved, and the rate capability 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 direct contact between the matrix material and 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 positive electrode material + A transmission channel, which improves the ionic conductivity of the material and Li relative to other fast non-electrochemically active ionic conductors 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring capacity loss of materials 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% or 98%, etc.
Preferably, the mass fraction of the coating layer material is 2-10%, for example: 2%, 4%, 6%, 8% or 10%, etc.
In a second aspect, the present invention provides a method for preparing the lithium iron manganese phosphate positive electrode material according to the first aspect, the method comprising 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, performing one-step reaction to obtain a first precipitate, and performing one-step sintering treatment on the obtained precipitate to obtain a porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor material obtained in the step (1) with a lithium source, and performing two-step sintering treatment to obtain a matrix material;
(3) Mixing a vanadium source, a lithium source and a solvent, adding the matrix material obtained in the step (2) to obtain a suspension, adding a second phosphorus source, performing a two-step reaction to obtain a second precipitate, and performing three-step sintering treatment on the second precipitate to obtain the lithium iron manganese phosphate anode material.
In the preparation process of the lithium iron manganese phosphate anode material, the organic carbon source is cracked and oxidized by oxygen in the sintering process to generate carbon dioxide and water to form a loose porous structure, so that electrolyte can enter the internal holes, the migration rate of lithium ions can be effectively improved, and the rate capability is improved.
Preferably, the iron source of step (1) comprises at least one of ferrous sulphate, 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 doped metal source 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 monoammonium 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% or 35%, etc.
Preferably, the temperature of the one-step reaction of step (1) is 20 to 50 ℃, for example: 20 ℃, 25 ℃,30 ℃, 40 ℃ or 50 ℃ and the like.
Preferably, the one-step reaction time is 3 to 8 hours, for example: 3h, 4h, 5h, 6h, 7h or 8h, etc.
Preferably, the solid obtained after the one-step reaction is subjected to suction filtration, washing, water washing and drying.
Preferably, the temperature of the one-step sintering process is 500 to 750 ℃, for example: 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 750 ℃, etc.
Preferably, the one-step sintering treatment is performed for 2 to 5 hours, for example: 2h, 2.5h, 3h, 4h or 5h, etc.
Preferably, the two-step sintering treatment of step (2) includes primary sintering and secondary sintering.
Preferably, the temperature of the primary sintering is 200 to 300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃ or 300 ℃ and the like.
Preferably, the time of the primary sintering is 3 to 5 hours, for example: 3h, 3.5h, 4h, 4.5h, 5h, etc.
Preferably, the temperature of the secondary sintering is 600 to 800 ℃, for example: 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, etc.
Preferably, the secondary sintering time is 8 to 15 hours, for example: 8h, 9h, 10h, 12h or 15h, etc.
Preferably, the vanadium source of step (2) comprises ammonium metavanadate and/or vanadium pentoxide.
Preferably, the second phosphorus source comprises ammonium phosphate and/or monoammonium phosphate.
Preferably, the temperature of the two-step reaction is 20 to 50 ℃, for example: 20 ℃, 25 ℃,30 ℃, 40 ℃ or 50 ℃ and the like.
Preferably, the two-step reaction takes 3 to 8 hours, for example: 3h, 4h, 5h, 6h, 7h or 8h, etc.
Preferably, the solid obtained after the two-step reaction is subjected to suction filtration, washing, water washing and drying.
Preferably, the atmosphere of the three-step sintering process 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 sintering and four sintering.
Preferably, the temperature of the three sintering is 200 to 300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃ or 300 ℃ and the like.
Preferably, the time of the three times of sintering is 3 to 5 hours, for example: 3h, 3.5h, 4h, 4.5h, 5h, etc.
Preferably, the temperature of the four times of sintering is 600 to 800 ℃, for example: 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, etc.
Preferably, the time of the four times of sintering is 8 to 15 hours, for example: 8h, 9h, 10h, 12h or 15h, etc.
In a third aspect, the invention provides a positive electrode sheet, which is characterized in that the positive electrode sheet comprises the lithium iron manganese phosphate positive electrode material according to the first aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet 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 meanwhile, the matrix material is doped with other elements, so that defects are generated in the crystal, and the defects are beneficial to Li + And because of different charge valence states, a charge difference is generated, cation vacancies are formed through a charge compensation mechanism, the conductivity of the material is improved, and the rate performance 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, so that a loose porous structure is formed, and therefore, the electrolyte can enter the inner holes, the migration rate of lithium ions can be effectively improved, and the rate capability is improved. While Li is 3 V 2 (PO 4 ) 3 The coating of the material prevents the direct contact between the matrix material and 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 positive electrode material + A transmission channel, which improves the ionic conductivity of the material and Li relative to other fast non-electrochemically active ionic conductors 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring capacity loss of materials due to coating.
(2) The first discharge specific capacity of the lithium iron manganese phosphate anode material prepared into the battery with 5C multiplying power can reach more than 151mAh/g, and the capacity retention rate can reach more than 89% after the lithium iron manganese phosphate anode material is cycled for 2000 times under 3C multiplying power.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: ti=0.86: 0.1: mixing ferrous sulfate, manganese nitrate and titanium chloride uniformly in deionized water, adding ammonium phosphate and glucose (the mass of the glucose is 20% of that of a precursor material) while stirring, reacting for 6 hours at 35 ℃, carrying out suction filtration on a product, washing until the pH value of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, and then preserving the dried precipitate sample at 650 ℃ for 3 hours to obtain a loose and porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material for 4 hours at the temperature of 250 ℃ before sintering for 10 hours at the temperature of 700 ℃ to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 6 hours at 30 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering at 250 ℃ for 4 hours under inert atmosphere, and sintering at 700 ℃ for 12 hours to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 95%, and the mass ratio of the coating layer material is 5%.
Example 2
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: ti=0.85: 0.11: mixing ferrous sulfate, manganese nitrate and titanium chloride uniformly in deionized water, adding ammonium phosphate and glucose (the mass of the glucose is 25% of that of a precursor material) while stirring, reacting for 6 hours at 40 ℃, carrying out suction filtration on a product, washing until the pH value of washing water is neutral, placing a precipitate at 95 ℃ for vacuum drying for 28 hours, and then preserving the dried precipitate sample at 600 ℃ for 3 hours to obtain a loose and porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 280 ℃ for 4 hours, and then sintering at 720 ℃ for 10 hours to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 6 hours at 30 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 95 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering for 4 hours at 280 ℃ in an inert atmosphere, and sintering for 12 hours at 720 ℃ to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 94%, and the mass ratio of the coating layer material is 6%.
Example 3
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: ti=0.79: 0.20: mixing ferrous sulfate, manganese nitrate and titanium chloride uniformly in deionized water, adding ammonium phosphate and sucrose (the mass of sucrose is 35% of that of a precursor material) while stirring, reacting for 3 hours at 50 ℃, carrying out suction filtration on a product, washing until the pH value of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, and then preserving the heat of the dried precipitate sample at 500 ℃ for 5 hours to obtain a loose porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material at 200 ℃ for 5 hours, and then sintering at 600 ℃ for 15 hours to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering at 200 ℃ for 5 hours under inert atmosphere, and sintering at 600 ℃ for 15 hours to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 90%, and the mass ratio of the coating layer material is 10%.
Example 4
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: zr=0.90: 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 that of a precursor material) 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, and then carrying out heat preservation on the dried precipitate sample at 550 ℃ for 5 hours to obtain a loose porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering the mixed material for 4.5 hours at 220 ℃ before sintering for 12 hours at 650 ℃ to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering at 200 ℃ for 5 hours under inert atmosphere, and sintering at 650 ℃ for 12 hours to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 92%, and the mass ratio of the coating layer material is 8%.
Example 5
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: zr=0.82: 0.15: mixing ferrous sulfate, manganese nitrate and zirconium chloride uniformly in deionized water, adding ammonium phosphate and starch (the mass of the starch is 18% of that of a precursor material) while stirring, reacting for 7 hours at 25 ℃, carrying out suction filtration on a product, washing until the pH value of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, and then preserving the dried precipitate sample at 700 ℃ for 2.5 hours to obtain a loose and porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering 4.h the mixed material at the temperature of 250 ℃ and then sintering for 12 hours at the temperature of 750 ℃ to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering at 250 ℃ for 4 hours under inert atmosphere, and sintering at 750 ℃ for 10 hours to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 92%, and the mass ratio of the coating layer material is 8%.
Example 6
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: al=0.82: 0.16: 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 7 hours at 25 ℃, then carrying out suction filtration on the product, washing until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, and then preserving the dried precipitate sample at 750 ℃ for 2.5 hours to obtain a loose porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering 4.h the mixed material at the temperature of 250 ℃ and then sintering for 12 hours at the temperature of 750 ℃ to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering at 300 ℃ for 4 hours under inert atmosphere, and sintering at 800 ℃ for 10 hours to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 98%, and the mass ratio of the coating layer material is 2%.
Example 7
The embodiment provides a lithium iron manganese phosphate positive electrode material, which is prepared by the following steps:
(1) According to the mole ratio of Fe: mn: al=0.75: 0.20: 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 that of a precursor material) while stirring, reacting for 7 hours at 25 ℃, carrying out suction filtration on a product, washing until the pH value of washing water is neutral, placing a precipitate at 90 ℃ for vacuum drying for 25 hours, and then preserving the dried precipitate sample at 650 ℃ for 2.5 hours to obtain a loose and porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor obtained in the step (1) with lithium carbonate, grinding, spray drying, sintering 4.h the mixed material at 280 ℃ and then sintering for 12 hours at 700 ℃ to obtain a matrix material;
(3) Uniformly mixing ammonium metavanadate and lithium carbonate in deionized water, mixing according to the molar ratio of the ammonium metavanadate to the lithium carbonate of 4:3, adding the matrix material obtained in the step (2) into the mixed solution, stirring to form uniform suspension, adding ammonium phosphate while stirring, reacting for 8 hours at 20 ℃, carrying out suction filtration and washing on the product until the pH value of washing water is neutral, placing the precipitate at 90 ℃ for vacuum drying for 25 hours, transferring the dried precipitate into an atmosphere furnace, sintering for 4 hours at 280 ℃ in an inert atmosphere, and sintering for 10 hours at 700 ℃ to obtain the positive electrode material, wherein the mass ratio of the matrix material in the positive electrode material is 93%, and the mass ratio of the coating layer material is 7%.
Comparative example 1
This comparative example differs from example 1 only in that no doping metal source was added, and other conditions and parameters were exactly the same as 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 example 1.
Comparative example 3
This comparative example differs from example 1 only in that no coating layer was added, and other conditions and parameters were exactly the same as example 1.
Performance test:
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 each prepared in a ratio of 90:5:5 in a solvent of N-methylpyrrolidone (NMP), preparing a positive electrode mixture, and applying the mixture on an aluminum foil, and drying the resultant, and then rolling to prepare a positive electrode;
artificial graphite, conductive agent (Super PTM), carboxymethyl cellulose and styrene-butadiene rubber were mixed with 92:4:2:2 in a weight ratio of NMP to prepare a negative electrode mixture, coating the negative electrode mixture on a copper foil, drying the prepared product, and then rolling to prepare a negative electrode;
an electrode assembly was prepared by placing a porous polyethylene separator between the above-prepared positive electrode and negative electrode, placing the electrode assembly in a case, and then injecting an electrolyte 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)/ethylmethyl carbonate (EMC) (mixed volume ratio of EC/DMC/emc=3/4/3).
2. Testing of the Properties of the Positive electrode Material
Charging the lithium secondary battery with 1C at 25 ℃ under constant current/constant voltage (CC/CV) conditions until 4.2V/0.05C, then discharging to 3.0V using 5C under Constant Current (CC) conditions, and calculating a specific discharge capacity;
the lithium secondary battery was charged with 3C at 25 ℃ under constant current/constant voltage (CC/CV) conditions until 4.2V/0.05C, and then discharged to 3.0V using 3C under Constant Current (CC) conditions. With this as one cycle, the test was repeated for 2000 cycles. The capacity retention rate of the 2000 th cycle during charge and discharge was measured.
The test results are shown in Table 1
TABLE 1
As can be seen from Table 1, according to examples 1 to 7, the initial discharge specific capacity of the lithium iron manganese phosphate anode material prepared into a battery with 5C multiplying power can be more than 151mAh/g, and the capacity retention rate after the material is circulated for 2000 times under 3C multiplying power can be more than 89%.
In the preparation process of the lithium iron manganese phosphate positive electrode material, the addition amount of the organic carbon source can influence the performance of the lithium iron manganese phosphate positive electrode material, the weight of the organic carbon source is controlled to be 15-35% of the weight of the final prepared ferric phosphate precursor material, the prepared lithium iron manganese phosphate positive electrode material has good performance, and if the addition amount of the organic carbon source is too low, an effective conductive network can be difficult to form, so that the improvement effect of C on the material is reduced; if the organic carbon source is excessively added, the prepared positive electrode material has the problems of low compacted density and low gram capacity.
As can be seen from the comparison of example 1 and comparative example 1, the present invention dopes transition metal in lithium manganese iron phosphate positive electrode material, and doping causes defects in the crystal, which are beneficial to Li + And because of different charge valence states, a charge difference is generated, cation vacancies are formed through a charge compensation mechanism, the conductivity of the material is improved, and the rate performance of the material is improved.
The comparison between the embodiment 1 and the comparative example 2 shows that the organic carbon source is cracked and oxidized to generate carbon dioxide and water when meeting oxygen in the heat preservation process to form a loose porous structure, so that the electrolyte can enter the inner holes, the migration rate of lithium ions can be effectively improved, and the multiplying power performance is improved.
As can be seen from the comparison of example 1 and comparative example 3, li 3 V 2 (PO 4 ) 3 Coating of material, preventing electrolysis of the base materialLiquid direct contact, reduce Mn dissolution, facilitate improving material cycle performance, and Li 3 V 2 (PO 4 ) 3 Is a fast ion conductor material which increases Li on the surface of the positive electrode material + A transmission channel, which improves the ionic conductivity of the material and Li relative to other fast non-electrochemically active ionic conductors 3 V 2 (PO 4 ) 3 Has better electrochemical activity and voltage platform, and can not bring capacity loss of materials due to coating.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (35)
1. The lithium manganese iron phosphate anode material is characterized by comprising a matrix material and a coating layer material arranged on the surface of the matrix material, wherein the matrix material has a porous structure, and the chemical formula of the matrix 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 more than or equal to 0.01 and less than or equal to 0.05, and the lithium iron manganese phosphate anode material is prepared by the following method:
(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, performing one-step reaction to obtain a first precipitate, and performing one-step sintering treatment on the obtained precipitate to obtain a porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor material obtained in the step (1) with a lithium source, and performing two-step sintering treatment to obtain a matrix material;
(3) Mixing a vanadium source, a lithium source and a solvent, adding the matrix material obtained in the step (2) to obtain a suspension, adding a second phosphorus source, performing a two-step reaction to obtain a second precipitate, and performing three-step sintering treatment on the second precipitate to obtain the lithium iron manganese phosphate anode material;
and (3) cracking and oxidizing the organic carbon source in the step (1) in the presence of oxygen in the heat preservation process to generate carbon dioxide and water, so as to form a loose porous structure.
2. The lithium iron manganese phosphate positive electrode material according to claim 1, wherein the coating material comprises lithium vanadium phosphate.
3. The lithium iron manganese phosphate positive electrode material according to claim 1, wherein the mass fraction of the matrix material is 90-98% based on 100% of the mass of the lithium iron manganese phosphate positive electrode material.
4. The lithium iron manganese phosphate anode material according to claim 1, wherein the mass fraction of the coating layer material is 2-10%.
5. A method for preparing the lithium iron manganese phosphate positive electrode material according to any one of claims 1 to 4, 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, performing one-step reaction to obtain a first precipitate, and performing one-step sintering treatment on the obtained precipitate to obtain a porous ferric phosphate precursor material;
(2) Mixing the ferric phosphate precursor material obtained in the step (1) with a lithium source, and performing two-step sintering treatment to obtain a matrix material;
(3) Mixing a vanadium source, a lithium source and a solvent, adding the matrix material obtained in the step (2) to obtain a suspension, adding a second phosphorus source, performing a two-step reaction to obtain a second precipitate, and performing three-step sintering treatment on the second precipitate to obtain the lithium iron manganese phosphate anode material.
6. The method of claim 5, wherein the source of iron in step (1) comprises at least one of ferrous sulfate, ferrous chloride, ferric nitrate, or ferrous oxalate.
7. The method of manufacturing of claim 5, wherein the manganese source comprises at least one of manganous sulfate, manganous chloride, or manganous nitrate.
8. The method of preparing of claim 5, wherein the doped metal source comprises at least one of titanium sulfate, titanium chloride, titanium nitrate, zirconium sulfate, zirconium chloride, zirconium nitrate, aluminum sulfate, aluminum chloride, or aluminum nitrate.
9. The method of claim 5, wherein the first phosphorus source comprises ammonium phosphate and/or monoammonium phosphate.
10. The method of claim 5, wherein the organic carbon source comprises at least one of glucose, sucrose, starch, maltose, or polyethylene glycol.
11. The method according to claim 5, wherein the mass of the organic carbon source is 15 to 35% based on 100% of the mass of the iron phosphate precursor material.
12. The method of claim 5, wherein the temperature of the one-step reaction in step (1) is 20 to 50 ℃.
13. The method of claim 5, wherein the one-step reaction is performed for 3 to 8 hours.
14. The process according to claim 5, wherein the solid obtained after the one-step reaction is subjected to suction filtration, washing, water washing and drying.
15. The method according to claim 5, wherein the temperature of the one-step sintering treatment is 500-750 ℃.
16. The method according to claim 5, wherein the one-step sintering treatment is performed for 2 to 5 hours.
17. The method of claim 5, wherein the two-step sintering process of step (2) comprises a primary sintering and a secondary sintering.
18. The method of claim 17, wherein the primary sintering is performed at a temperature of 200-300 ℃.
19. The method of claim 17, wherein the time of the primary sintering is 3 to 5 hours.
20. The method of claim 17, wherein the secondary sintering is performed at a temperature of 600-800 ℃.
21. The method of claim 17, wherein the secondary sintering is performed for 8 to 15 hours.
22. The method of claim 5, wherein the vanadium source of step (2) comprises ammonium metavanadate and/or vanadium pentoxide.
23. The method of claim 5, wherein the second phosphorus source comprises ammonium phosphate and/or monoammonium phosphate.
24. The method according to claim 5, wherein the temperature of the two-step reaction is 20 to 50 ℃.
25. The method of claim 5, wherein the two-step reaction is performed for 3 to 8 hours.
26. The process according to claim 5, wherein the solid obtained after the two-stage reaction is subjected to suction filtration, washing, water washing and drying.
27. The method of claim 5, wherein the atmosphere of the three-step sintering process is an inert atmosphere.
28. The method of claim 27, wherein the inert atmosphere comprises at least one of nitrogen, helium, or argon.
29. The method of manufacturing according to claim 5, wherein the three-step sintering process comprises three times of sintering and four times of sintering.
30. The method of claim 29, wherein the temperature of the three sintering is 200-300 ℃.
31. The method of claim 29, wherein the three times of sintering are 3 to 5 hours.
32. The method of claim 29, wherein the temperature of the four sintering is 600-800 ℃.
33. The method of claim 29, wherein the four times of sintering are 8 to 15 hours.
34. A positive electrode sheet, characterized in that it comprises the lithium iron manganese phosphate positive electrode material according to any one of claims 1 to 4.
35. A lithium ion battery comprising the positive electrode sheet of claim 34.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210885550.0A CN115020685B (en) | 2022-07-26 | 2022-07-26 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210885550.0A CN115020685B (en) | 2022-07-26 | 2022-07-26 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115020685A CN115020685A (en) | 2022-09-06 |
| CN115020685B true CN115020685B (en) | 2023-09-01 |
Family
ID=83080315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210885550.0A Active CN115020685B (en) | 2022-07-26 | 2022-07-26 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115020685B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872384A (en) * | 2022-12-14 | 2023-03-31 | 湖北亿纬动力有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN117133920B (en) * | 2023-10-25 | 2023-12-29 | 成都仪隆电子有限公司 | Modified lithium iron manganese phosphate anode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094163A1 (en) * | 2015-12-03 | 2017-06-08 | 株式会社東芝 | Positive electrode active material for nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, nonaqueous electrolyte battery, and battery pack |
| CN110783546A (en) * | 2019-11-04 | 2020-02-11 | 桑顿新能源科技有限公司 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode slurry and positive electrode, lithium ion battery and equipment |
| CN111477862A (en) * | 2020-05-11 | 2020-07-31 | 何家均 | Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN114156475A (en) * | 2021-11-09 | 2022-03-08 | 安徽博石高科新材料股份有限公司 | Lithium vanadium phosphate composite modified lithium manganate material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201323322A (en) * | 2011-12-13 | 2013-06-16 | Hirose Tech Co Ltd | Porous lithium phosphate metal salt and method for preparing the same |
-
2022
- 2022-07-26 CN CN202210885550.0A patent/CN115020685B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094163A1 (en) * | 2015-12-03 | 2017-06-08 | 株式会社東芝 | Positive electrode active material for nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, nonaqueous electrolyte battery, and battery pack |
| CN110783546A (en) * | 2019-11-04 | 2020-02-11 | 桑顿新能源科技有限公司 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode slurry and positive electrode, lithium ion battery and equipment |
| CN111477862A (en) * | 2020-05-11 | 2020-07-31 | 何家均 | Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN114156475A (en) * | 2021-11-09 | 2022-03-08 | 安徽博石高科新材料股份有限公司 | Lithium vanadium phosphate composite modified lithium manganate material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115020685A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115020685B (en) | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof | |
| CN109301174B (en) | Positive electrode material, method for producing same, and lithium secondary battery | |
| CN105514378B (en) | A kind of imitative eucaryotic cell structure anode composite material of lithium sulfur battery and preparation method thereof | |
| CN113659146B (en) | Potassium-lanthanum-silicon ternary co-doped sodium vanadium phosphate electrode material, and preparation method and application thereof | |
| CN110104677B (en) | Composite lithium titanate material and preparation method and application thereof | |
| CN111463419A (en) | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof | |
| CN114242988A (en) | Positive electrode material and preparation method and application thereof | |
| CN115064665B (en) | Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof | |
| CN111646459A (en) | Preparation method and application of boron-doped graphene material | |
| CN112952047A (en) | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN114388738B (en) | Silicon-based anode material and preparation method and application thereof | |
| CN110061311B (en) | Preparation method of solid electrolyte layer for water-based zinc battery | |
| CN115101738A (en) | Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof | |
| CN114141981A (en) | Positive pole piece and preparation method and application thereof | |
| CN111668448B (en) | Lithium iron phosphate modified composite material and preparation method thereof | |
| CN112768664A (en) | Preparation method of ruthenium-doped lithium iron phosphate composite positive electrode material | |
| CN114976025B (en) | Positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery | |
| CN116344763A (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN116417598A (en) | Iron-based polyanion type sodium ion battery positive electrode material and preparation method thereof | |
| CN113526552B (en) | Composite positive electrode active material of lithium ion battery and preparation method thereof | |
| CN113526485B (en) | Porous sodium vanadium fluorophosphate composite material regulated and controlled by carbon quantum dots and preparation method and application thereof | |
| CN114751395A (en) | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN113113588A (en) | Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy | |
| CN114751391B (en) | High-density phosphorylated sodium titanate material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |