CN114709391B - Positive electrode lithium supplementing material, preparation method thereof and lithium ion battery - Google Patents
Positive electrode lithium supplementing material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN114709391B CN114709391B CN202210347811.3A CN202210347811A CN114709391B CN 114709391 B CN114709391 B CN 114709391B CN 202210347811 A CN202210347811 A CN 202210347811A CN 114709391 B CN114709391 B CN 114709391B
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- Prior art keywords
- lithium
- positive electrode
- source
- sintering
- electrode lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 130
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 118
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000011149 active material Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 45
- 239000002244 precipitate Substances 0.000 claims description 26
- 235000015165 citric acid Nutrition 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 15
- 229930006000 Sucrose Natural products 0.000 claims description 13
- 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 13
- 239000005720 sucrose Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 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 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 229910002706 AlOOH Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 229930091371 Fructose Natural products 0.000 claims description 9
- 239000005715 Fructose Substances 0.000 claims description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 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 7
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- 239000002019 doping agent Substances 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 5
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 claims description 5
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 5
- 229960002413 ferric citrate Drugs 0.000 claims description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229940032950 ferric sulfate Drugs 0.000 claims description 3
- 229960001781 ferrous sulfate Drugs 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 239000011267 electrode slurry Substances 0.000 abstract description 18
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000005253 cladding Methods 0.000 abstract description 7
- 239000011247 coating layer Substances 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 17
- 239000011572 manganese Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical compound [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 235000011044 succinic acid Nutrition 0.000 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 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: (1) Heating, drying and sintering a solution containing a lithium source, an iron source and a doped metal source to obtain an LFMO precursor; (2) Mixing aluminum sol with the LFMO precursor obtained in the step (1), and calcining to obtain the positive electrode lithium supplementing material. The preparation method of the positive electrode lithium supplementing material provided by the invention obtains the positive electrode lithium supplementing material with an internal doping and external cladding structure; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is affected.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials of lithium ion batteries, relates to a preparation method of a positive electrode lithium supplementing material, and particularly relates to a positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery.
Background
The current commonly used lithium ion negative electrode material is graphite, the capacity of the lithium ion negative electrode material has reached the limit, and in order to improve the energy density of the battery, the silicon-based negative electrode material with high specific capacity becomes the negative electrode material of the commercial lithium ion battery of the next generation with the highest potential. However, the silicon-based negative electrode has serious volume effect and lower first coulombic efficiency in the charge and discharge process, however, the first coulombic efficiency of the positive electrode material is far higher than that of the negative electrode, the low first effect of the negative electrode causes the loss of recyclable lithium, and the capacity of the battery is reduced, so the concept of lithium supplementation is generated.
The positive electrode lithium supplementing is to add a lithium supplementing material as an additive in the positive electrode homogenate process, and when the battery core is charged and discharged for the first time after the battery core is manufactured, the positive electrode lithium supplementing material has higher gram capacity and lower initial effect, a large amount of lithium ions are removed in the normal charging process to supplement lithium ions consumed by the negative electrode to form an SEI film, and a large amount of lithium ions are not accepted in the discharging process due to lower initial effect, so that the capacity of the battery is improved.
At present, the pre-lithiation technology capable of realizing industrialization is lithium coating of metal lithium foil, but because the metal lithium is too active, a relatively low dew point (-45 ℃) is needed, the lithium foil calendaring equipment is relatively expensive, the positive electrode lithium supplementing agent can be pre-lithiated only by being added into the slurry according to a normal manufacturing process flow, but the positive electrode lithium supplementing agent is relatively sensitive to moisture, liOH is formed on the surface after water absorption, and the fluorine-containing binder is extremely easy to be attacked by alkaline groups to generate crosslinking reaction, so that the slurry is gelled.
In addition, the lithium supplementing agent LFO material generates a large amount of combustible gas under the catalysis of a surface structure in the high-voltage formation lithium removing process, the catalysis effect of the surface structure on the electrolyte can be relieved by changing the surface composition and the structure of the material, the surface composition of the material is changed by metal doping, and the contact area between the surface active layer and the electrolyte is reduced by surface cladding, so that the technical problems of gelation, gas production and the like are solved.
CN 105206779a discloses a ceramic diaphragm, which is coated with a layer of Li based on the existing base film 2 MnO 3 、Li 2 MnO 3 -LiNiCoMnO 2 、Li 5 FeO 4 、Li 5 Fe 5 O 8 The method can supplement lithium in the charging and discharging process, but the cost of equipment, process and materials is increased in the process of coating the compound on the diaphragm, and the performances of tensile strength, air permeability, porosity and the like of the diaphragm are changed after the diaphragm is coated.
CN 107863567a Li doped with conductive metal 2 The O powder is used for preparing a positive electrode lithium supplementing material, so that the lithium supplementing effect can be achieved, and the battery capacity is further improved, but in actual use, the positive electrode lithium supplementing material is characterized in that Li 2 The trace amount of water in O (and water to produce strong base LiOH) and N-methylpyrrolidone (NMP) is liable to cause PVDF decomposition and deactivation, resulting in coagulation of the positive electrode slurry, failure of coating, and then Li of the insulator even in very severe anhydrous environment 2 O can cause incomplete decomposition in the first charging lithium supplementing process, and gas can still be generated in the using process of the battery, so that the safety problem is caused by the gas expansion and rupture of the battery.
Therefore, how to prevent gelation and a large amount of combustible gas generated after adding the positive electrode lithium supplementing material into the positive electrode slurry, which causes difficult application of the positive electrode slurry and serious influence on the safety of the battery, is a technical problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery, and the positive electrode lithium supplementing material with an internal doping and external cladding structure is obtained; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is affected.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a positive electrode lithium-supplementing material, the method comprising the steps of:
(1) Heating, drying and sintering a solution containing a lithium source, an iron source and a doped metal source to obtain an LFMO precursor;
(2) Mixing aluminum sol with the LFMO precursor obtained in the step (1), and calcining to obtain the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material provided by the invention obtains the positive electrode lithium supplementing material with an internal doping and external cladding structure; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is affected.
Preferably, the molar ratio of lithium source, iron source and dopant metal source in the solution of step (1) is Li: fe: M=5 (1-x): x, where 0 < x.ltoreq.0.01, for example, may be 0.0005, 0.001, 0.002, 0.005, 0.007, 0.009 or 0.0099, but is not limited to the values recited, other non-recited values within the range of values being equally applicable, preferably 0.002 < x.ltoreq.0.01.
The molar ratio Li: fe: M of the lithium source, the iron source and the doped metal source refers to the molar ratio of Li atoms in the lithium source, fe atoms in the iron source and doped metal atoms M in the doped metal source.
Preferably, the concentration of the lithium source in the solution in step (1) is 0.5-2mol/L, for example, 0.5mol/L, 0.6mol/L, 1mol/L, 1.5mol/L, 1.8mol/L or 2mol/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the lithium source of step (1) comprises any one or a combination of at least two of anhydrous lithium hydroxide, lithium monohydrate, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate or lithium oxide, typically but not limitatively comprises a combination of anhydrous lithium hydroxide and lithium monohydrate, a combination of lithium monohydrate and lithium carbonate, a combination of lithium carbonate and lithium acetate, a combination of lithium acetate and lithium borate, a combination of lithium borate and lithium metaborate, a combination of lithium metaborate and lithium lactate, a combination of lithium lactate and lithium nitrate, a combination of lithium nitrate and lithium oxalate, a combination of lithium oxalate and lithium oxide, a combination of anhydrous lithium hydroxide and lithium monohydrate, lithium carbonate, a combination of lithium acetate, lithium borate and lithium metaborate, or a combination of lithium lactate, lithium nitrate, lithium oxalate and lithium oxide.
Preferably, the iron source of step (1) comprises any one or a combination of at least two of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, or ferric citrate, typically but not limited to a combination comprising ferric nitrate and ferrous nitrate, a combination of ferrous nitrate and ferric chloride, a combination of ferric chloride and ferrous chloride, a combination of ferrous chloride and ferric sulfate, a combination of ferric sulfate and ferrous sulfate, a combination of ferrous sulfate and ferric citrate, a combination of ferric nitrate, ferrous nitrate and ferric chloride, or a combination of ferrous chloride, ferric sulfate, ferrous sulfate, and ferric citrate.
Preferably, the doping metal of step (1) comprises any one or a combination of at least two of Al, nb, co, mn, ni, mo, ru or Cr, typically but not limited to a combination of Al and Nb, a combination of Nb and Co, a combination of Co and Mn, a combination of Mn and Ni, a combination of Ni and Mo, a combination of Mo and Ru, a combination of Ru and Cr, a combination of Al, nb and Co, a combination of Nb, co, mn and Ni, or a combination of Co, mn, ni, mo and Ru, preferably Mn.
Preferably, the doping metal source of step (1) comprises any one or a combination of at least two of a chloride, sulfate or nitrate of a doping metal, typically but not limited to a combination of a chloride and sulfate of a doping metal, a combination of a sulfate and nitrate of a doping metal, a combination of a chloride and nitrate of a doping metal, or a combination of a chloride, sulfate and nitrate of a doping metal.
According to the invention, the catalysis of lithium ferrite to electrolyte at a potential of more than 3.6V can be effectively inhibited by doping metal, so that the generation of combustible gas, such as obviously reduced hydrogen ratio in gas production, is reduced, and the safety of battery production is greatly improved.
Preferably, the heating time in step (1) is 10-60min, for example, 10min, 20min, 30min, 40min, 50min or 60min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the heating temperature in the step (1) is 45-98 ℃, for example, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the method of drying of step (1) comprises spray drying.
Preferably, the sintering in step (1) includes a first sintering and a second sintering performed sequentially.
Preferably, the atmosphere of the first sintering comprises an air atmosphere.
Preferably, the time of the first sintering is 3-10h, for example, 3h, 5h, 7h, 9h or 10h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the first sintering is 500-700 ℃, for example, 500 ℃, 520 ℃, 550 ℃, 600 ℃, 650 ℃, 680 ℃, or 700 ℃, but the temperature is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the atmosphere of the second sintering includes a protective gas atmosphere.
Preferably, the shielding gas comprises nitrogen and/or an inert gas.
Preferably, the second sintering time is 5-10h, for example, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the temperature of the second sintering is 700-900 ℃, for example, 700 ℃, 720 ℃, 750 ℃, 800 ℃, 850 ℃, 880 ℃, or 900 ℃, but the second sintering is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the aluminium sol of step (2) comprises AlOOH.
Preferably, the aluminum sol contains a carbon source.
Preferably, the mass ratio of AlOOH to carbon source is (9-12): 1, which may be, for example, 9:1, 9.5:1, 10:1, 11.5:1 or 12:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the preparation method of the aluminum sol in the step (2) comprises the following steps:
(i) Mixing ammonia water and aluminum salt to obtain a solution containing precipitate;
(ii) Mixing an organic acid, a carbon source and the solution containing the precipitate obtained in step (i) to obtain the aluminum sol.
In the preparation method provided by the invention, carbon-containing aluminum sol is used for carrying out surface coating on the lithium ferrite doped with metal; double coating of carbon and metal oxide is realized at one time by a sol method, so that the problem that the contact reaction surface of uncoated lithium ferrite, moisture in air and carbon dioxide is alkaline is solved, and the generation of gelation of anode slurry is avoided.
The aluminum oxide coating layer is coated on the surface of the positive electrode lithium supplementing material, so that the residual alkali amount on the surface of the material is reduced, and meanwhile, the coating of certain carbon can effectively inhibit side reactions between the material and electrolyte, so that the safety performance of the lithium ion battery is improved.
According to the invention, the sp2 carbon-coated positive electrode lithium supplementing material is obtained through coating the carbon-source-containing aluminum sol, and the conductivity is better.
Preferably, the ratio of ammonia water to aluminum salt in step (i) is (3-6): 1, which may be, for example, 3:1, 3.5:1, 4:1, 5:1, 5.5:1 or 6:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. The unit of the liquid-solid ratio is mL/g.
Preferably, the organic acid of step (ii) comprises citric acid.
Preferably, the carbon source of step (ii) comprises an organic carbon source.
Preferably, the organic carbon source comprises any one or a combination of at least two of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid, or acetic acid, typically, but not limited to, a combination of glucose and fructose, a combination of fructose and sucrose, a combination of sucrose and soluble starch, a combination of soluble starch and succinic acid, a combination of succinic acid and citric acid, a combination of citric acid and lactic acid, a combination of lactic acid and acetic acid, a combination of glucose, fructose and sucrose, a combination of fructose, sucrose and soluble starch, a combination of sucrose, soluble starch, succinic acid and citric acid, a combination of citric acid, lactic acid and acetic acid, a combination of fructose, sucrose, soluble starch and succinic acid, or a combination of sucrose, soluble starch, succinic acid, citric acid and lactic acid.
Preferably, the mass of the organic acid in step (ii) is 0.01-2wt% of the solution containing the precipitate, which may be, for example, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt% or 2wt%, but is not limited to the values recited, other non-recited values within the range of values are equally applicable.
Preferably, the mass of the carbon source in step (ii) is 0.1-0.5wt% of the solution containing the precipitate, which may be, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% or 0.5wt%, but is not limited to the values recited, other non-recited values within the range of values being equally applicable.
Preferably, the molar ratio of the alumina sol of step (2) to the LFMO precursor of step (1) is 0.01 to 0.1, and may be, for example, 0.01, 0.02, 0.05, 0.07, 0.08 or 0.1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the calcination of step (2) is carried out under an inert atmosphere.
Preferably, the shielding gas comprises nitrogen and/or an inert gas.
Preferably, the temperature of the calcination in step (2) is 450-600deg.C, which may be, for example, 450deg.C, 480deg.C, 500deg.C, 550deg.C, 580 deg.C or 600deg.C, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the calcination in step (2) is performed for a period of time ranging from 2 to 10 hours, such as 2 hours, 3 hours, 5 hours, 7 hours, 9 hours or 10 hours, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferred technical scheme of the preparation method according to the first aspect of the present invention, the preparation method comprises the following steps:
(1) Heating, spray drying and sintering a solution containing a lithium source, an iron source and a doped metal source, wherein the sintering comprises a first sintering and a second sintering, the first sintering is performed in an air atmosphere for 3-10h at 500-700 ℃, the second sintering is performed in an inert gas atmosphere for 5-10h at 700-900 ℃ to obtain an LFMO precursor;
the molar ratio of the lithium source, the iron source and the doped metal source in the solution is Li: fe: M=5 (1-x): x, wherein x is more than 0 and less than 0.01;
(2) Mixing aluminum sol and the LFMO precursor obtained in the step (1) in a molar ratio of 0.01-0.1, and calcining for 2-10h in nitrogen and/or inert atmosphere at a calcining temperature of 450-600 ℃ to obtain the positive electrode lithium supplementing material;
the preparation method of the aluminum sol comprises the following steps:
(i) Mixing ammonia water and aluminum salt with the liquid-solid ratio of (3-6) being 1 to obtain solution containing sediment;
(ii) Mixing citric acid, an organic carbon source and the solution containing the precipitate obtained in the step (i) to obtain the aluminum sol;
the organic carbon source comprises any one or a combination of at least two of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid or acetic acid;
the mass of the citric acid is 0.01-2wt% of the solution containing the precipitate;
the mass of the organic carbon source is 0.1-0.5wt% of the solution containing the precipitate.
In a second aspect, the invention provides a positive electrode lithium supplementing material, which is obtained by the preparation method in the first aspect.
Preferably, the positive electrode lithium supplementing material comprises an active material and a surface coating;
preferably, the active material has the chemical formula Li 5 Fe 1-x M x O 4 Wherein 0 < x.ltoreq.0.01, M comprises any one or a combination of at least two of Al, nb, co, mn, ni, mo, ru or Cr.
Preferably, the particle diameter D of the positive electrode lithium supplementing material 50 For example, the value is not more than 3. Mu.m, and may be 0.1. Mu.m, 0.2. Mu.m, 0.5. Mu.m, 1. Mu.m, 2. Mu.m, or 3. Mu.m, but the present invention is not limited to the values recited, and other values not recited in the numerical range are applicable.
Preferably, the surface coating comprises Al 2 O 3 。
Preferably, in the positive electrode lithium supplementing material, al 2 O 3 With Li 5 Fe 1-x M x O 4 The molar ratio of (2) is 0.005-0.05, and may be, for example, 0.005, 0.01, 0.025, 0.03, 0.035, 0.04 or 0.05, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable, preferably 0.005-0.02.
Preferably, carbon is also included in the surface coating.
Preferably, the mass of the carbon is 0.2-5wt% of the positive electrode lithium supplementing material, for example, 0.2wt%, 1wt%, 2wt%, 2.5wt%, 4wt% or 5wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 0.2-3.5wt%.
In a third aspect, the present invention provides a lithium ion battery comprising the positive electrode lithium-supplementing material according to the second aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method of the positive electrode lithium supplementing material provided by the invention obtains the positive electrode lithium supplementing material with an internal doping and external cladding structure; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is affected.
(2) In the preparation method provided by the invention, carbon-containing aluminum sol is used for carrying out surface coating on the lithium ferrite doped with metal; double coating of carbon and metal oxide is realized at one time by a sol method, so that the problem that the contact reaction surface of uncoated lithium ferrite, moisture in air and carbon dioxide is alkaline is solved, and the generation of gelation of anode slurry is avoided.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. 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 positive electrode lithium supplementing material, D 50 Is 3 mu m, and the positive electrode lithium supplementing material comprises an active material Li 5 Fe 0.995 Mn 0.005 O 4 And a surface coating comprising Al 2 O 3 And C; al (Al) 2 O 3 With Li 5 Fe 0.995 Mn 0.005 O 4 The molar ratio of (2) is 0.02; the mass of the carbon accounts for 2.5wt% of the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material comprises the following steps:
(1) Heating a solution containing anhydrous lithium hydroxide, ferric nitrate and manganese chloride with a molar ratio of Li to Fe, mn=5:0.995:0.005 at 75 ℃ for 35min, wherein the concentration of a lithium source in the solution is 1mol/L, performing spray drying on the heated solution to obtain a mixture precursor, performing two times of sintering on the mixture precursor, wherein the first sintering is performed in an air atmosphere for 6h at 600 ℃, the second sintering is performed in an inert gas atmosphere for 8h at 800 ℃, and obtaining the LFMO precursor;
(2) Mixing aluminum sol and the LFMO precursor obtained in the step (1) in a molar ratio of 0.02, and calcining for 7 hours in an inert atmosphere at a calcining temperature of 500 ℃ to obtain the positive electrode lithium supplementing material;
the aluminum sol comprises AlOOH and a carbon source in a mass ratio of 10:1.
The preparation method of the aluminum sol comprises the following steps:
(i) Mixing ammonia water and aluminum nitrate in a liquid-solid ratio of 4.5:1 to obtain a solution containing precipitate;
(ii) Mixing citric acid, glucose and the solution containing the precipitate obtained in the step (i), wherein the mass of the citric acid is 1wt% of the solution containing the precipitate, and the mass of the glucose is 0.3wt% of the solution containing the precipitate, so as to obtain the aluminum sol.
Example 2
The embodiment provides a positive electrode lithium supplementing material, D 50 Is 2 mu m, and the positive electrode lithium supplementing material comprises an active material Li 5 Fe 0.999 Mn 0.001 O 4 And a surface coating comprising Al 2 O 3 And C; al (Al) 2 O 3 With Li 5 Fe 0.999 Mn 0.001 O 4 The molar ratio of (2) was 0.1. The mass of the carbon accounts for 5wt% of the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material comprises the following steps:
(1) Heating a solution containing lithium hydroxide monohydrate, ferrous nitrate and manganese sulfate with a molar ratio of Li to Fe, mn=5:0.999:0.001 at 45 ℃ for 60min, wherein the concentration of a lithium source in the solution is 0.5mol/L, performing spray drying on the heated solution to obtain a mixture precursor, performing two times of sintering on the mixture precursor, wherein the first sintering is performed in an air atmosphere for 3h at 700 ℃, and the second sintering is performed in an inert gas atmosphere for 5h at 900 ℃ to obtain an LFMO precursor;
(2) Mixing aluminum sol and the LFMO precursor obtained in the step (1) in a molar ratio of 0.01, and calcining for 2 hours in an inert atmosphere at a temperature of 600 ℃ to obtain the positive electrode lithium supplementing material;
the aluminum sol comprises AlOOH and a carbon source, wherein the mass ratio of the AlOOH to the carbon source is 9:1.
The preparation method of the aluminum sol comprises the following steps:
(i) Mixing ammonia water and aluminum nitrate in a liquid-solid ratio of 3:1 to obtain a solution containing precipitate;
(ii) Mixing citric acid, succinic acid and the solution containing the precipitate obtained in the step (i), wherein the mass of the citric acid is 0.01 weight percent of the solution containing the precipitate, and the mass of the succinic acid is 0.1 weight percent of the solution containing the precipitate, so as to obtain the aluminum sol.
Example 3
The embodiment provides a positive electrode lithium supplementing material, D 50 Is 2.5 mu m, and the positive electrode lithium supplementing material comprises an active material Li 5 Fe 0.99 Mn 0.01 O 4 And a surface coating comprising Al 2 O 3 And C; al (Al) 2 O 3 With Li 5 Fe 0.99 Mn 0.01 O 4 The molar ratio of (2) is 0.01; the mass of the carbon accounts for 0.5wt% of the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material comprises the following steps:
(1) Heating a solution containing lithium carbonate, ferric chloride and manganese nitrate with a molar ratio of Li to Fe, mn=5:0.99:0.01 at 98 ℃ for 10min, wherein the concentration of a lithium source in the solution is 2mol/L, performing spray drying on the heated solution to obtain a mixture precursor, performing two times of sintering on the mixture precursor, wherein the first sintering is performed in an air atmosphere for 10h at 500 ℃, and the second sintering is performed in an inert gas atmosphere for 10h at 700 ℃ to obtain an LFMO precursor;
(2) Mixing aluminum sol and the LFMO precursor obtained in the step (1) in a molar ratio of 0.01, and calcining for 10 hours in an inert atmosphere at a calcining temperature of 450 ℃ to obtain the positive electrode lithium supplementing material;
the aluminum sol comprises AlOOH and a carbon source, wherein the mass ratio of the AlOOH to the carbon source is 12:1.
The preparation method of the aluminum sol comprises the following steps:
(i) Mixing ammonia water and aluminum nitrate in a liquid-solid ratio of 6:1 to obtain a solution containing precipitate;
(ii) Mixing citric acid, sucrose and the solution containing the precipitate obtained in the step (i), wherein the mass of the citric acid is 2wt% of the solution containing the precipitate, and the mass of the sucrose is 0.5wt% of the solution containing the precipitate, so as to obtain the aluminum sol.
Example 4
The embodiment provides a positive electrode lithium supplementing material, which comprises an active material Li 5 Fe 0.995 Co 0.005 O 4 And a surface coating comprising Al 2 O 3 And C; al (Al) 2 O 3 With Li 5 Fe 0.995 Co 0.005 O 4 The molar ratio of (2) is 0.02; the mass of the carbon accounts for 2.5wt% of the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material comprises the following steps of the same process as in the example 1 except that manganese chloride is replaced by cobalt chloride with the same molar quantity.
Example 5
The embodiment provides a positive electrode lithium supplementing material, which comprises an active material Li 5 Fe 0.995 Ni 0.005 O 4 And a surface coating comprising Al 2 O 3 And C; al (Al) 2 O 3 With Li 5 Fe 0.995 Ni 0.005 O 4 The molar ratio of (2) is 0.02; the mass of the carbon accounts for 2.5wt% of the positive electrode lithium supplementing material.
The preparation method of the positive electrode lithium supplementing material comprises the following steps of the same process as in the example 1 except that manganese chloride is replaced by nickel chloride with the same molar quantity.
Example 6
The embodiment provides a positive electrode lithium supplementing material, except for Li: fe: mn=5:0.985:0.015 in the preparation method, wherein the active material in the positive electrode lithium supplementing material is Li 5 Fe 0.985 Mn 0.015 O 4 The remaining process steps were the same as in example 1.
Example 7
The present example provides a positive electrode lithium-compensating material, which was the same as example 1 except that the mass of glucose in the preparation method was adjusted to 0.08wt% of the precipitation-containing solution, so that the mass of carbon in the positive electrode lithium-compensating material was 0.3wt% of the positive electrode lithium-compensating material.
Example 8
The present example provides a positive electrode lithium-compensating material, which was the same as example 1 except that the mass of glucose in the preparation method was adjusted to 0.6wt% of the precipitation-containing solution, so that the mass of carbon in the positive electrode lithium-compensating material was 5.5wt% of the positive electrode lithium-compensating material.
Example 9
The embodiment provides a positive electrode lithium supplementing material, which is prepared by mixing aluminum sol and LFMO precursor obtained in the step (1) in a molar ratio of 0.05:1, so that Al 2 O 3 With Li 5 Fe 0.995 Mn 0.005 O 4 The remainder was the same as in example 1, except that the molar ratio of (2) was 0.05:1.
Example 10
The embodiment provides a positive electrode lithium supplementing material, which is prepared by mixing aluminum sol and LFMO precursor obtained in the step (1) in a molar ratio of 0.12:1, so that Al 2 O 3 With Li 5 Fe 0.995 Mn 0.005 O 4 The procedure of example 1 was followed except that the molar ratio of (C) was 0.12:1.
Example 11
The embodiment provides a positive electrode lithium supplementing material, which is prepared by mixing aluminum sol and LFMO precursor obtained in the step (1) in a molar ratio of 0.008:1, so that Al 2 O 3 With Li 5 Fe 0.995 Mn 0.005 O 4 Is of the mole of (2)The remainder was the same as in example 1, except that the molar ratio was 0.008:1.
Example 12
The present example provides a positive electrode lithium-supplementing material, which is the same as in example 1 except that the aluminum sol in step (2) does not contain a carbon source, and glucose is not added in step (ii) in the preparation method of the aluminum sol.
Example 13
This example provides a positive electrode lithium-supplementing material, which is the same as in example 1 except that only the first sintering is performed in step (2) and no second sintering is performed.
Example 14
This example provides a positive electrode lithium-supplementing material, which is the same as in example 1 except that only the second sintering is performed in step (2) without the first sintering.
Comparative example 1
This comparative example provides a positive electrode lithium-supplementing material, the remainder being the same as in example 1, except that no doping metal source is added in step (1).
Comparative example 2
This comparative example provides a positive electrode lithium-supplementing material, the remainder being the same as in example 1, except that no aluminum sol is mixed in step (2).
Comparative example 3
The comparative example provides a positive electrode lithium supplementing material, except that in the preparation method, the ferric nitrate is replaced by nickel nitrate, so that the active material is Li 2 Ni 0.995 Mn 0.005 O 2 The procedure of example 1 was repeated except that the other components were the same.
And mixing the positive electrode lithium supplementing material with the positive electrode material to obtain positive electrode slurry, coating, cold pressing, die cutting and slitting to obtain a positive electrode plate, and assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte into the lithium ion battery. The solid content and viscosity of the positive electrode slurry were tested. And charging the obtained lithium ion battery with 0.1C current in the formation stage, testing the volumes of all gases generated in the formation process of the soft-packed battery at intervals of 10% SOC in the range of 10-100% SOC, and calculating the gas generation volume change. Wherein, the gas production volume change = gas production volume of a battery added with a positive electrode lithium supplement material/gas production volume of a battery without a lithium supplement agent. All produced gas is collected in the process of formation and partial volume, GC-MS test is carried out, the volume content of the combustible gas is detected, the ratio of the combustible gas to the total produced gas is calculated, and the obtained result is shown in table 1.
TABLE 1
| Test number | Solid content | Viscosity (mPa S) | Gas production volume variation | Duty cycle of combustible gas |
| Example 1 | 62％ | 13000 | 1.5 | 3％ |
| Example 2 | 62％ | 14000 | 1.45 | 2.80％ |
| Example 3 | 62％ | 24000 | 2.5 | 5％ |
| Example 4 | 62％ | 13500 | 1.55 | 3.50％ |
| Example 5 | 62％ | 13800 | 1.6 | 3.30％ |
| Example 6 | 62％ | 13700 | 1.55 | 2.50％ |
| Example 7 | 62％ | 14500 | 1.7 | 2.75％ |
| Example 8 | 62％ | 14200 | 1.45 | 2.80％ |
| Example 9 | 62％ | 13800 | 1.4 | 2.60％ |
| Example 10 | 62％ | 13200 | 1.38 | 2.50％ |
| Example 11 | 62％ | 30000 | 3 | 6％ |
| Example 12 | 62％ | 15200 | 2.6 | 3.10％ |
| Example 13 | 62％ | 14100 | 3 | 6％ |
| Example 14 | 62％ | 13800 | 4 | 5.50％ |
| Comparative example 1 | 62％ | 13200 | 10 | 72％ |
| Comparative example 2 | 62％ | 42000 | - | - |
| Comparative example 3 | 62％ | 14200 | 7 | 50％ |
Remarks: the gas yield is the ratio relative to the volume without the addition of lithium supplement.
From table 1 the following conclusions are drawn:
(1) The preparation method of the positive electrode lithium supplementing material provided by the invention can obtain the positive electrode lithium supplementing material with an internal doping and external cladding structure from examples 1-5 and comparative examples 1-2; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is affected.
(2) As is clear from a comparison of example 6 with example 1, when the molar amount of the doping metal is not in the range of 0 < x.ltoreq.0.01, x > 0.01, the viscosity and the combustible gas do not change much, and the doping ions decrease the capacity of the material by changing the structure of the material, resulting in a decrease in lithium supplementing efficiency. .
(3) As is clear from comparison of examples 7 and 8 with example 1, when the carbon coating amount is not in the range of 0.5 to 5wt%, the conductivity of the lithium supplementing agent is lowered when the carbon coating amount is less than 0.5wt%, the positive electrode lithium supplementing material is added into the positive electrode slurry, the lithium supplementing gas yield is increased without increasing the combustible gas ratio, and when the carbon coating amount is more than 5wt%, the effect on gas yield is not great, but the lithium supplementing efficiency of the material is lowered.
(4) From examples 9 to 11 and example 1As a comparison, when Al 2 O 3 With Li 5 Fe 1-x Mn x O 4 When the molar ratio of (2) is not in the range of 0.01-0.1, the viscosity of the positive electrode lithium supplementing material added into the positive electrode slurry increases when the alumina ratio is less than 0.01, the gas yield increases, the combustible gas ratio increases, the explosion limit is higher, the safety performance is lowered, and when the alumina ratio is more than 0.1, the viscosity increases, but the lithium supplementing efficiency of the lithium supplementing agent is reduced, preferably 0.01-0.04.
(5) As is clear from a comparison of example 12 and example 1, when there is no carbon doping in the aluminum sol, the viscosity of the positive electrode lithium supplementing material added to the positive electrode slurry does not change much, but the conductivity of the lithium supplementing agent is reduced, resulting in an increase in the gas yield of the combustible gas and a decrease in safety performance.
(6) As is clear from comparison of examples 13 and 14 with example 1, when the sintering is not performed step by step in step (2), the viscosity of the positive electrode lithium supplementing material added to the positive electrode slurry does not change much, the gas yield and the combustible gas ratio are increased, and the safety performance is lowered.
(7) As is clear from comparison of comparative example 1 and example 1, when no metal is doped, the viscosity of the positive electrode lithium supplementing material added into the positive electrode slurry is unchanged, the gas yield is increased by 10 times, the combustible gas ratio is increased, and the safety performance is extremely low.
(8) As is clear from a comparison between comparative example 2 and example 1, when the coating is not performed, the viscosity of the positive electrode lithium-compensating material increases when it is added to the positive electrode slurry, and a gel is formed, and the battery cannot be manufactured by coating.
(9) As is clear from a comparison of comparative example 3 and example 1, when Fe is replaced with Ni, the viscosity of the positive electrode lithium supplementing material added to the positive electrode slurry is unchanged, the gas yield is increased, the combustible gas ratio is increased, the safety limit is exceeded, and the safety performance is extremely low.
In summary, the preparation method of the positive electrode lithium supplementing material provided by the invention obtains the positive electrode lithium supplementing material with an internal doping and external cladding structure; the problem of higher gas production ratio when lithium ferrite is used as a positive electrode lithium supplementing agent is solved by doping metal for modification; by coating the surface of the lithium supplementing agent active material with an alumina coating layer, the residual alkali amount on the surface of the material is reduced, and agglomeration in the positive electrode slurry is avoided, so that the safety of the lithium ion battery is influenced; in the preparation method, carbon-containing aluminum sol is used for carrying out surface coating on the lithium ferrite doped with metal; double coating of carbon and metal oxide is realized at one time by a sol method, so that the problem that the contact reaction surface of uncoated lithium ferrite, moisture in air and carbon dioxide is alkaline is solved, and the generation of gelation of anode slurry is avoided.
The process flow of the present invention is described by the above embodiments, but the present invention is not limited to the above process flow, i.e., it does not mean that the present invention must be implemented by the above process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (42)
1. The preparation method of the positive electrode lithium supplementing material is characterized by comprising the following steps of:
(1) Heating, drying and sintering a solution containing a lithium source, an iron source and a doped metal source to obtain an LFMO precursor;
(2) Mixing aluminum sol with the molar ratio of 0.01-0.1 and the LFMO precursor obtained in the step (1), wherein the aluminum sol comprises AlOOH, the aluminum sol contains a carbon source, the mass ratio of the AlOOH to the carbon source is (9-12): 1, and calcining to obtain the positive electrode lithium supplementing material;
the positive electrode lithium supplementing material comprises an active material and a surface coating; the surface coating further comprises carbon; the chemical formula of the active material is Li 5 Fe 1-x M x O 4 Wherein 0 < x.ltoreq.0.01, M comprises any one or a combination of at least two of Al, nb, co, mn, ni, mo, ru or Cr.
2. The method according to claim 1, wherein the molar ratio of the lithium source, the iron source and the dopant metal source in the solution of step (1) is Li: fe: M=5 (1-x): x, wherein 0 < x.ltoreq.0.01.
3. The method according to claim 2, wherein the molar ratio of the lithium source, the iron source and the dopant metal source in the solution of step (1) is Li: fe: M=5 (1-x): x, wherein 0.002 < x.ltoreq.0.01.
4. The method of claim 1, wherein the concentration of the lithium source in the solution of step (1) is 0.5 to 2mol/L.
5. The method of claim 1, wherein the lithium source of step (1) comprises any one or a combination of at least two of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate, or lithium oxide.
6. The method of claim 1, wherein the iron source of step (1) comprises any one or a combination of at least two of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, or ferric citrate.
7. The method of claim 1, wherein the doping metal of step (1) comprises any one or a combination of at least two of Al, nb, co, mn, ni, mo, ru or Cr.
8. The method of claim 1, wherein the dopant metal source of step (1) comprises any one or a combination of at least two of a chloride, sulfate, or nitrate of dopant metal.
9. The method of claim 1, wherein the heating in step (1) is for a period of 10 to 60 minutes.
10. The method of claim 1, wherein the heating in step (1) is at a temperature of 45-98 ℃.
11. The method of claim 1, wherein the method of drying in step (1) comprises spray drying.
12. The method of claim 1, wherein the sintering in step (1) comprises a first sintering and a second sintering performed sequentially.
13. The method of preparing according to claim 12, wherein the atmosphere of the first sintering comprises an air atmosphere.
14. The method of claim 12, wherein the first sintering is for a period of 3 to 10 hours.
15. The method of claim 12, wherein the first sintering temperature is 500-700 ℃.
16. The method of manufacturing according to claim 12, wherein the atmosphere of the second sintering comprises a protective gas atmosphere.
17. The method of claim 16, wherein the shielding gas comprises nitrogen and/or an inert gas.
18. The method of claim 12, wherein the second sintering is performed for a period of time ranging from 5 to 10 hours.
19. The method of claim 12, wherein the second sintering temperature is 700-900 ℃.
20. The method of claim 1, wherein the method of preparing the aluminum sol of step (2) comprises:
(i) Mixing ammonia water and aluminum salt to obtain a solution containing precipitate;
(ii) Mixing an organic acid, a carbon source and the solution containing the precipitate obtained in step (i) to obtain the aluminum sol.
21. The method according to claim 20, wherein the ratio of the aqueous ammonia to the aluminum salt in the step (i) is (3-6): 1.
22. The method of claim 20, wherein the organic acid of step (ii) comprises citric acid.
23. The method of claim 20, wherein the carbon source of step (ii) comprises an organic carbon source.
24. The method of claim 23, wherein the organic carbon source comprises any one or a combination of at least two of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid, or acetic acid.
25. The method of claim 20, wherein the organic acid in step (ii) is present in an amount of 0.01 to 2wt% based on the solution containing the precipitate.
26. The method of claim 20, wherein the mass of the carbon source in step (ii) is 0.1 to 0.5wt% of the solution containing the precipitate.
27. The method according to claim 1, wherein the calcination in step (2) is performed in a protective gas atmosphere.
28. The method of claim 27, wherein the shielding gas comprises nitrogen and/or an inert gas.
29. The method of claim 1, wherein the calcination in step (2) is carried out at a temperature of 450-600 ℃.
30. The method of claim 1, wherein the calcination in step (2) is for a period of 2 to 10 hours.
31. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Heating, spray drying and sintering a solution containing a lithium source, an iron source and a doped metal source to obtain an LFMO precursor; the sintering comprises a first sintering and a second sintering, wherein the first sintering is performed in an air atmosphere for 3-10 hours at 500-700 ℃, and the second sintering is performed in an inert gas atmosphere for 5-10 hours at 700-900 ℃;
the molar ratio of the lithium source, the iron source and the doped metal source in the solution is Li, fe, M=5, (1-x) x, wherein x is more than 0 and less than or equal to 0.01;
(2) Mixing aluminum sol and the LFMO precursor obtained in the step (1) in a molar ratio of 0.01-0.1, and calcining for 2-10h in nitrogen and/or inert atmosphere at a calcining temperature of 450-600 ℃ to obtain the positive electrode lithium supplementing material;
the preparation method of the aluminum sol comprises the following steps:
(i) Mixing ammonia water and aluminum salt with the liquid-solid ratio of (3-6) being 1 to obtain solution containing sediment;
(ii) Mixing citric acid, an organic carbon source and the solution containing the precipitate obtained in the step (i) to obtain the aluminum sol;
the organic carbon source comprises any one or a combination of at least two of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid or acetic acid;
the mass of the citric acid is 0.01-2wt% of the solution containing the precipitate;
the mass of the organic carbon source is 0.1-0.5wt% of the solution containing the precipitate.
32. A positive electrode lithium supplementing material, characterized in that the positive electrode lithium supplementing material is obtained by the preparation method according to any one of claims 1 to 31.
33. The positive electrode lithium-compensating material of claim 32, wherein the positive electrode lithium-compensating material comprises an active material and a surface coating.
34. The positive electrode lithium-supplementing material according to claim 33, wherein the active material has a chemical formula of Li 5 Fe 1-x M x O 4 Wherein 0 < x.ltoreq.0.01, M comprises any one or a combination of at least two of Al, nb, co, mn, ni, mo, ru or Cr.
35. The positive electrode lithium-supplementing material according to claim 32, wherein the positive electrode lithium-supplementing material has a particle diameter D 50 ≤3μm。
36. The positive electrode lithium-compensating material of claim 33, wherein the surface coating comprises Al 2 O 3 。
37. The positive electrode lithium-supplementing material according to claim 32, wherein, in the positive electrode lithium-supplementing material, al 2 O 3 With Li 5 Fe 1-x M x O 4 The molar ratio of (2) is 0.005-0.05.
38. The positive electrode lithium supplementing material according to claim 37, wherein in the positive electrode lithium supplementing material, al 2 O 3 With Li 5 Fe 1-x M x O 4 The molar ratio of (2) is 0.005-0.02.
39. The positive electrode lithium-compensating material of claim 33, wherein the surface coating further comprises carbon.
40. The positive electrode lithium-compensating material of claim 39, wherein the carbon is 0.2-5wt% of the positive electrode lithium-compensating material.
41. The positive electrode lithium-compensating material of claim 40, wherein the carbon is 0.2-3.5wt% of the positive electrode lithium-compensating material.
42. A lithium ion battery comprising the positive electrode lithium-supplementing material of any one of claims 32-41.
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