CN114709391A - Positive electrode lithium supplement material, preparation method thereof and lithium ion battery - Google Patents
Positive electrode lithium supplement material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN114709391A CN114709391A CN202210347811.3A CN202210347811A CN114709391A CN 114709391 A CN114709391 A CN 114709391A CN 202210347811 A CN202210347811 A CN 202210347811A CN 114709391 A CN114709391 A CN 114709391A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- sintering
- source
- supplement material
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 141
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000463 material Substances 0.000 title claims abstract description 110
- 239000013589 supplement Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011149 active material Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 46
- 239000002244 precipitate Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 235000015165 citric acid Nutrition 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 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
- 229910052593 corundum Inorganic materials 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
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 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
- 229920002472 Starch Polymers 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- 239000007787 solid Substances 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 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
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 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
- 229940040692 lithium hydroxide monohydrate Drugs 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
- 229910052804 chromium Inorganic materials 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
- 229940032950 ferric sulfate Drugs 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 229960001781 ferrous sulfate 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
- 229910052707 ruthenium Inorganic materials 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
- 239000000126 substance Substances 0.000 claims description 3
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006256 anode slurry Substances 0.000 abstract description 9
- 239000003513 alkali Substances 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
- 238000005253 cladding Methods 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011267 electrode slurry Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 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
- 230000015572 biosynthetic process Effects 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
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 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
- 239000007773 negative electrode material Substances 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
- 230000003197 catalytic effect Effects 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
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000007774 positive electrode material Substances 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
- 229910016955 Fe1-xMnx Inorganic materials 0.000 description 1
- 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
- 229910010699 Li5FeO4 Inorganic materials 0.000 description 1
- 229910015009 LiNiCoMnO2 Inorganic materials 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
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base 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
- 238000006555 catalytic reaction 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
- 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
- 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
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 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
- 239000010955 niobium Substances 0.000 description 1
- -1 or Co Substances 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
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
Abstract
The invention relates to a positive electrode lithium supplement 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) and (3) mixing the aluminum sol with the LFMO precursor obtained in the step (1), and calcining to obtain the positive electrode lithium supplement material. According to the preparation method of the positive electrode lithium supplement material, the positive electrode lithium supplement material with an inner doping and outer cladding structure is obtained; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, thereby influencing the safety of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, relates to a preparation method of an anode lithium supplement material, and particularly relates to the anode lithium supplement material, the preparation method of the anode lithium supplement material and a lithium ion battery.
Background
The currently common lithium ion negative electrode material is graphite, the capacity of the graphite reaches 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 next generation commercial lithium ion battery negative electrode material with the highest potential. However, the silicon-based negative electrode has a serious volume effect and a low first coulombic efficiency in the charge and discharge process, but the first coulombic efficiency of the positive electrode material is far higher than that of the negative electrode, and the low first efficiency of the negative electrode causes the loss of recyclable lithium and reduces the capacity of the battery, so the concept of lithium supplement is developed.
The positive pole lithium supplement is that the lithium supplement material is added as an additive in the positive pole homogenizing process, when the battery core is prepared and charged for the first time, the positive pole lithium supplement material has higher gram capacity and lower first effect, a large amount of lithium ions are separated in the normal charging process and are used for supplementing the lithium ions consumed by the SEI film formed by the negative pole, and a large amount of lithium ions cannot be accepted due to the lower first effect in the discharging process, so that the capacity of the battery is improved.
The lithium pre-lithiation technology capable of realizing industrialization at present is lithium-clad metal lithium foil, but the lithium metal is too active, a relatively low dew point (-45 ℃) is needed, lithium foil calendering equipment is expensive, a positive electrode lithium supplement agent only needs to be added into slurry to carry out pre-lithiation according to a normal manufacturing process flow, but the positive electrode lithium supplement agent is sensitive to moisture, LiOH is formed on the surface after water absorption, and a fluorine-containing binder is easily attacked by a basic group to carry out a crosslinking reaction so as to cause the slurry to be gelatinized.
In addition, the lithium supplement LFO material generates a large amount of combustible gas under the catalysis of a surface structure in the high-voltage formation and lithium removal process, the catalytic action 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 of a surface active layer and the electrolyte is reduced by surface coating, so that the technical problems of gelation, gas generation and the like are solved.
CN 105206779A discloses a ceramic diaphragm, which is coated with a layer of Li on the basis of the prior basal membrane2MnO3、Li2MnO3-LiNiCoMnO2、Li5FeO4、Li5Fe5O8The method can play a role in supplementing lithium in the charging and discharging process, but equipment, processes and materials are increased in the process of coating the compound on the diaphragmThe cost of the material and the properties of the diaphragm such as tensile strength, air permeability, porosity and the like can be changed after the diaphragm is coated.
CN 107863567A Li doped with conductive metal2The lithium supplementing material for the positive electrode prepared from O powder can play a role in supplementing lithium and further improve the battery capacity, but in actual use, due to Li2The reaction of trace amounts of water in O (which reacts with water to produce LiOH, a strong base) and N-methylpyrrolidone (NMP) tends to cause decomposition and deactivation of PVDF, leading to coagulation of the positive electrode slurry, failure to coat, and, secondly, Li of the insulator even if coated in a very harsh, anhydrous environment2O can lead to incomplete decomposition in the process of first charging and lithium supplementing, and gas can still be generated in the using process of the battery, so that the safety problem caused by the expansion and the rupture of the battery is caused.
Therefore, how to prevent the positive electrode slurry from being difficult to apply and seriously affect the safety of the battery due to gelation and generation of a large amount of combustible gas after the positive electrode lithium supplement material is added into the positive electrode slurry is a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the technical problems, the invention provides a positive electrode lithium supplement material, a preparation method thereof and a lithium ion battery, and the positive electrode lithium supplement material with an inner doping and outer cladding structure is obtained; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, thereby influencing the safety of the lithium ion battery.
In order 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 supplement material, wherein the 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) and (3) mixing the aluminum sol with the LFMO precursor obtained in the step (1), and calcining to obtain the positive electrode lithium supplement material.
According to the preparation method of the positive electrode lithium supplement material, the positive electrode lithium supplement material with an inner doping and outer cladding structure is obtained; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, thereby influencing the safety of the lithium ion battery.
Preferably, the molar ratio of lithium source, iron source and doping metal source in the solution of step (1) is Li: Fe: M ═ 5 (1-x): x, where 0 < x ≦ 0.01, and may be, for example, 0.0005, 0.001, 0.002, 0.005, 0.007, 0.009 or 0.0099, but is not limited to the recited values, and other values within the range of values are equally applicable, preferably 0.002 < x ≦ 0.01.
The molar ratio Li to Fe to M of the lithium source, the iron source and the doping metal source refers to the molar ratio of Li atoms in the lithium source, Fe atoms in the iron source and doping metal atoms M in the doping metal source.
Preferably, the concentration of the lithium source in the solution of step (1) is 0.5-2mol/L, and may be, for example, 0.5mol/L, 0.6mol/L, 1mol/L, 1.5mol/L, 1.8mol/L or 2mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the lithium source of step (1) comprises anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, any one or a combination of at least two of lithium nitrate, lithium oxalate or lithium oxide, typical but non-limiting combinations include a combination of anhydrous lithium hydroxide and lithium hydroxide monohydrate, a combination of lithium hydroxide 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 hydroxide 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 of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate or ferric citrate or a combination of at least two thereof, and typical but non-limiting combinations include a combination of 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, typical but non-limiting combinations include Al and Nb, Nb and Co, Co and Mn, Mn and Ni, Ni and Mo, Mo and Ru, Ru and Cr, Al, Nb and Co, Nb, Mn and Ni, or Co, Mn, Ni, Mo and Ru, preferably Mn.
Preferably, the source of the doping metal in step (1) comprises any one of or a combination of at least two of a chloride, sulfate or nitrate of the doping metal, and typical but non-limiting combinations include a chloride and sulfate combination of the doping metal, a sulfate and nitrate combination of the doping metal, a chloride and nitrate combination of the doping metal, or a chloride, sulfate and nitrate combination of the doping metal.
The invention can effectively inhibit the catalytic action of lithium ferrite on the electrolyte at the potential of more than 3.6V by doping metal, thereby reducing the generation of combustible gas, for example, the proportion of hydrogen in the produced gas is obviously reduced, and the safety of battery production is greatly improved.
Preferably, the heating time in step (1) is 10-60min, such as 10min, 20min, 30min, 40min, 50min or 60min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the heating temperature in step (1) is 45-98 deg.C, such as 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 98 deg.C, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the method of drying of step (1) comprises spray drying.
Preferably, the sintering of step (1) comprises a first sintering and a second sintering which are performed sequentially.
Preferably, the atmosphere of the first sintering comprises an air atmosphere.
Preferably, the time of the first sintering is 3 to 10 hours, for example, 3 hours, 5 hours, 7 hours, 9 hours or 10 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the first sintering is 500-700 ℃, for example, 500 ℃, 520 ℃, 550 ℃, 600 ℃, 650 ℃, 680 ℃ or 700 ℃, but not limited to the recited values, and other unrecited values in the range of values are also applicable.
Preferably, the atmosphere of the second sintering includes a protective gas atmosphere.
Preferably, the protective gas comprises nitrogen and/or an inert gas.
Preferably, the time of the second sintering is 5 to 10 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the second sintering is 700-900 ℃, for example 700 ℃, 720 ℃, 750 ℃, 800 ℃, 850 ℃, 880 ℃ or 900 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the aluminum sol of step (2) comprises AlOOH.
Preferably, the aluminum sol contains a carbon source.
Preferably, the mass ratio of AlOOH to the carbon source is (9-12):1, and 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 values not recited in the numerical range are also applicable.
Preferably, the preparation method of the aluminum sol in the step (2) is as follows:
(i) mixing ammonia water and aluminum salt to obtain a solution containing precipitate;
(ii) (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, the carbon-containing aluminum sol is used for coating the surface of the metal-doped lithium ferrite; the 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 iron oxide with moisture and carbon dioxide in the air is alkaline is solved, and the gelation of the anode slurry is avoided.
The surface of the anode lithium supplement material is coated with the alumina coating layer, so that the residual alkali amount on the surface of the material is reduced, and the coating of a certain amount of carbon can effectively inhibit the side reaction between the material and the electrolyte, thereby improving the safety performance of the lithium ion battery.
According to the invention, the sp2 carbon-coated positive electrode lithium supplement material is obtained by coating with carbon source-containing alumina sol, and the conductivity is better.
Preferably, the liquid-solid ratio of the ammonia water to the aluminum salt in step (i) is (3-6):1, and 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 enumerated values, and other unrecited values within the numerical range are also 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, typical but non-limiting combinations include 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 and succinic acid, a combination of 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 to 2 wt% of the solution containing the precipitate, which may be, for example, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, or 2 wt%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the mass of the carbon source in step (ii) is 0.1-0.5 wt% of the solution containing the precipitate, which may be, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the molar ratio of the aluminum sol of step (2) to the LFMO precursor of step (1) is 0.01 to 0.1, for example, 0.01, 0.02, 0.05, 0.07, 0.08 or 0.1, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the calcination of step (2) is carried out under an inert atmosphere.
Preferably, the protective gas comprises nitrogen and/or an inert gas.
Preferably, the temperature of the calcination in step (2) is 450-600 ℃, for example 450 ℃, 480 ℃, 500 ℃, 550 ℃, 580 ℃ or 600 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the calcination time in step (2) is 2-10h, such as 2h, 3h, 5h, 7h, 9h or 10h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, 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, wherein the sintering comprises first sintering and second sintering, the first sintering is carried out in an air atmosphere for 3-10h at the temperature of 500-900 ℃, the second sintering is carried out in an inert gas atmosphere for 5-10h at the temperature of 700-900 ℃, and an LFMO precursor is obtained;
the molar ratio of the lithium source, the iron source and the doping metal source in the solution is Li, Fe, M is 5 (1-x) x, wherein x is more than 0 and less than 0.01;
(2) mixing the aluminum sol with the LFMO precursor obtained in the step (1) in a molar ratio of 0.01-0.1, and calcining for 2-10h in a nitrogen and/or inert atmosphere at the temperature of 450-600 ℃ to obtain the anode lithium supplement material;
the preparation method of the aluminum sol comprises the following steps:
(i) ammonia water and aluminum salt with the mixed liquid-solid ratio of (3-6) to 1 to obtain a solution containing precipitate;
(ii) (ii) mixing citric acid, an organic carbon source and the solution containing the precipitate obtained in step (i) to obtain the aluminum sol;
the organic carbon source comprises any one or the 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 0.01-2 wt% of the solution containing the precipitate;
the mass of the organic carbon source is 0.1-0.5 wt% of the solution containing the precipitate.
In a second aspect, the invention provides a positive electrode lithium supplement material obtained by the preparation method of the first aspect.
Preferably, the positive lithium supplement material comprises an active material and a surface coating;
preferably, the active material has a chemical formula of Li5Fe1-xMxO4Wherein x is more than 0 and less than or equal to 0.01, and M comprises any one or the combination of at least two of Al, Nb, Co, Mn, Ni, Mo, Ru or Cr.
Preferably, the positive electrode lithium supplement material has a particle size D50Is less than 3 μmFor example, it may be 0.1. mu.m, 0.2. mu.m, 0.5. mu.m, 1. mu.m, 2. mu.m or 3 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the surface coating comprises Al2O3。
Preferably, in the positive electrode lithium supplement material, Al2O3With Li5Fe1-xMxO4The molar ratio of (B) is from 0.005 to 0.05, and may be, for example, from 0.005, 0.01, 0.025, 0.03, 0.035, 0.04 or 0.05, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably from 0.005 to 0.02.
Preferably, the surface coating further comprises carbon.
Preferably, the mass of the carbon is 0.2 to 5 wt% of the positive electrode lithium-supplementing material, and may be, for example, 0.2 wt%, 1 wt%, 2 wt%, 2.5 wt%, 4 wt%, or 5 wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, and preferably 0.2 to 3.5 wt%.
In a third aspect, the invention provides a lithium ion battery, which contains the positive electrode lithium supplement material as described in the second aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the preparation method of the positive electrode lithium supplement material, the positive electrode lithium supplement material with an inner doping and outer cladding structure is obtained; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, thereby influencing the safety of the lithium ion battery.
(2) In the preparation method provided by the invention, the carbon-containing aluminum sol is used for coating the surface of the metal-doped lithium ferrite; the 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 iron oxide with moisture and carbon dioxide in the air is alkaline is solved, and the gelation of the anode slurry is avoided.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive electrode lithium supplement material, and D of the positive electrode lithium supplement material50Is 3 μm, and the positive electrode lithium-supplementing material comprises active material Li5Fe0.995Mn0.005O4And a surface covering comprising Al2O3And C; al (Al)2O3With Li5Fe0.995Mn0.005O4Is 0.02; the mass of the carbon accounts for 2.5 wt% of the positive electrode lithium supplement material.
The preparation method of the positive electrode lithium supplement material comprises the following steps:
(1) heating a solution containing anhydrous lithium hydroxide, ferric nitrate and manganese chloride at a molar ratio of Li to Fe to Mn of 5:0.995:0.005 at 75 ℃ for 35min, wherein the concentration of a lithium source in the solution is 1mol/L, spray-drying the heated solution to obtain a mixture precursor, sintering the mixture precursor twice, performing first sintering in an air atmosphere for 6h at 600 ℃, performing second sintering in an inert gas atmosphere for 8h at 800 ℃ to obtain an LFMO precursor;
(2) mixing the aluminum sol with the LFMO precursor obtained in the step (1) according to a molar ratio of 0.02, and calcining for 7 hours in an inert atmosphere at the calcining temperature of 500 ℃ to obtain the anode lithium supplement 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 according to a liquid-solid ratio of 4.5:1 to obtain a solution containing precipitates;
(ii) (ii) mixing citric acid, glucose and the solution containing the precipitate obtained in step (i), wherein the mass of the citric acid is 1 wt% of the solution containing the precipitate, and the mass of the glucose is 0.3 wt% of the solution containing the precipitate, to obtain the aluminum sol.
Example 2
The embodiment provides a positive electrode lithium supplement material, and D of the positive electrode lithium supplement material50Is 2 μm, and the positive electrode lithium-supplementing material comprises active material Li5Fe0.999Mn0.001O4And a surface covering comprising Al2O3And C; al (Al)2O3With Li5Fe0.999Mn0.001O4Is 0.1. The mass of the carbon accounts for 5 wt% of the positive electrode lithium supplement material.
The preparation method of the positive electrode lithium supplement material comprises the following steps:
(1) heating a solution containing lithium hydroxide monohydrate, ferrous nitrate and manganese sulfate at a molar ratio of Li to Fe to Mn of 5 to 0.999 to 0.001 at 45 ℃ for 60min, wherein the concentration of a lithium source in the solution is 0.5mol/L, carrying out spray drying on the heated solution to obtain a mixture precursor, sintering the mixture precursor twice, carrying out first sintering in an air atmosphere at the temperature of 700 ℃ for 3h, and carrying out second sintering in an inert gas atmosphere at the temperature of 900 ℃ for 5h to obtain an LFMO precursor;
(2) mixing alumina sol and the LFMO precursor obtained in the step (1) according to a molar ratio of 0.01, and calcining for 2 hours in an inert atmosphere at the calcining temperature of 600 ℃ to obtain the anode lithium supplement 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 according to a liquid-solid ratio of 3:1 to obtain a solution containing a precipitate;
(ii) (ii) mixing citric acid, succinic acid and the solution containing the precipitate obtained in step (i), the mass of citric acid being 0.01 wt% of the solution containing the precipitate, and the mass of succinic acid being 0.1 wt% of the solution containing the precipitate, to obtain the aluminum sol.
Example 3
The embodiment providesA positive electrode lithium supplement material, D of the positive electrode lithium supplement material50Is 2.5 μm, and the positive electrode lithium-supplementing material comprises active material Li5Fe0.99Mn0.01O4And a surface covering comprising Al2O3And C; al (Al)2O3With Li5Fe0.99Mn0.01O4Is 0.01; the mass of the carbon accounts for 0.5 wt% of the positive electrode lithium supplement material.
The preparation method of the positive electrode lithium supplement material comprises the following steps:
(1) heating a solution containing lithium carbonate, ferric chloride and manganese nitrate with the molar ratio of Li to Fe to Mn being 5:0.99:0.01 at 98 ℃ for 10min, wherein the concentration of a lithium source in the solution is 2mol/L, carrying out spray drying on the heated solution to obtain a mixture precursor, sintering the mixture precursor twice, carrying out first sintering in an air atmosphere for 10h at 500 ℃, carrying out second sintering in an inert gas atmosphere for 10h at 700 ℃ to obtain an LFMO precursor;
(2) mixing the aluminum sol with the LFMO precursor obtained in the step (1) according to a molar ratio of 0.01, and calcining for 10 hours in an inert atmosphere at the temperature of 450 ℃ to obtain the anode lithium supplement 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 according to a liquid-solid ratio of 6:1 to obtain a solution containing a precipitate;
(ii) and (ii) mixing citric acid, sucrose and the solution containing the precipitate obtained in the step (i), wherein the mass of the citric acid is 2 wt% of the solution containing the precipitate, and the mass of the sucrose is 0.5 wt% of the solution containing the precipitate, so as to obtain the aluminum sol.
Example 4
The embodiment provides a positive electrode lithium supplement material which comprises an active material Li5Fe0.995Co0.005O4And a surface covering comprising Al2O3And C; al (aluminum)2O3With Li5Fe0.995Co0.005O4Is 0.02; the mass of the carbon accounts for 2.5 wt% of the positive electrode lithium supplement material.
The preparation method of the positive electrode lithium supplement material is the same as the example 1 except that the manganese chloride is replaced by cobalt chloride with equal molar quantity.
Example 5
The embodiment provides a positive electrode lithium supplement material which comprises an active material Li5Fe0.995Ni0.005O4And a surface covering comprising Al2O3And C; al (Al)2O3With Li5Fe0.995Ni0.005O4Is 0.02; the mass of the carbon accounts for 2.5 wt% of the positive electrode lithium supplement material.
The preparation method of the positive electrode lithium supplement material is the same as that of the embodiment 1 except that the manganese chloride is replaced by nickel chloride with equal molar quantity.
Example 6
This example provides a positive electrode lithium supplement material, where except that in the preparation method, Li: Fe: Mn is 5:0.985:0.015, and in the positive electrode lithium supplement material, an active material is Li5Fe0.985Mn0.015O4Otherwise, the remaining process steps are the same as in example 1.
Example 7
This example provides a positive electrode lithium supplement material, which is the same as that of example 1, except that the mass of glucose in the preparation method is adjusted to 0.08 wt% of the solution containing the precipitate, and the mass of carbon in the positive electrode lithium supplement material is adjusted to 0.3 wt% of the positive electrode lithium supplement material.
Example 8
This example provides a positive electrode lithium supplement material, which is the same as in example 1, except that the mass of glucose in the preparation method is adjusted to 0.6 wt% of the solution containing the precipitate, and the mass of carbon in the positive electrode lithium supplement material is adjusted to 5.5 wt% of the positive electrode lithium supplement material.
Example 9
This example provides a positive electrode lithium-supplementing material, which is obtained by mixing an aluminum sol and the LFMO precursor obtained in step (1) at a molar ratio of 0.05:1, and adding Al2O3With Li5Fe0.995Mn0.005O4The same as in example 1 except that the molar ratio of (B2) was 0.05: 1.
Example 10
This example provides a positive electrode lithium-supplementing material, which is obtained by mixing an aluminum sol and the LFMO precursor obtained in step (1) at a molar ratio of 0.12:1, and adding Al2O3With Li5Fe0.995Mn0.005O4The same as in example 1 except that the molar ratio of (A) to (B) was 0.12: 1.
Example 11
This example provides a positive electrode lithium supplement material, which is obtained by mixing an aluminum sol and the LFMO precursor obtained in step (1) at a molar ratio of 0.008:1 to obtain Al2O3With Li5Fe0.995Mn0.005O4The same as in example 1 except that the molar ratio of (B2) was 0.008: 1.
Example 12
This example provides a positive electrode lithium supplement material, which is the same as example 1 except that the alumina sol in step (2) does not contain a carbon source, and glucose is not added in step (ii) of the preparation method of the alumina sol.
Example 13
This example provides a positive electrode lithium-doped material, which is the same as example 1 except that only the first sintering is performed in step (2) without the second sintering.
Example 14
This example provides a positive electrode lithium-doped material, which is the same as 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 supplement material, which was the same as example 1 except that no doped metal source was added in step (1).
Comparative example 2
This comparative example provides a positive electrode lithium supplement material, which was the same as example 1 except that no aluminum sol was mixed in step (2).
Comparative example 3
The comparative example provides a positive electrode lithium supplement material, in which the active material is Li except that ferric nitrate is replaced by nickel nitrate in the preparation method2Ni0.995Mn0.005O2Otherwise, the same procedure as in example 1 was repeated.
And mixing the positive electrode lithium supplement material with a positive electrode material to obtain positive electrode slurry, coating, cold pressing, die cutting and slitting to obtain a positive electrode piece, and assembling the positive electrode piece, a negative electrode piece, a diaphragm and electrolyte into the lithium ion battery. The solid content and viscosity of the positive electrode slurry were measured. And charging the obtained lithium ion battery at a formation stage by 0.1C current, testing the volume of all gases generated in the formation and grading process of the soft package battery at intervals of 10% SOC within the range of 10-100% SOC, and calculating the change of the gas generation volume. Wherein, the gas production volume change is the gas production volume of the battery with the added positive electrode lithium supplement material/the gas production volume of the battery without the added lithium supplement agent. All the produced gas is collected in the chemical component content process and subjected to GC-MS test, the volume content of the combustible gas is detected, the combustible gas ratio, namely the volume of the combustible gas/the total produced gas volume, is calculated, and the obtained results are shown in Table 1.
TABLE 1
| Test number | Solid content | Viscosity (mPa S) | Volumetric change of gas production | Ratio 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％ |
Remarking: the gas yield is the ratio of the volume of the lithium supplement agent which is not added.
The following conclusions are drawn from table 1:
(1) the preparation method of the positive electrode lithium supplement material provided by the invention can obtain the positive electrode lithium supplement material with an inner doping and outer cladding structure from the examples 1-5 and the comparative examples 1-2; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, thereby influencing the safety of the lithium ion battery.
(2) As is clear from comparison between example 6 and example 1, when the molar amount of the doping metal is not in the range of 0 < x.ltoreq.0.01 and x > 0.01, the viscosity and combustible gas do not change so much, and the doping ions change the material structure to lower the capacity of the material, resulting in a decrease in the lithium replenishment efficiency. .
(3) It is understood from the comparison between examples 7 and 8 and example 1 that, when the amount of carbon coating is not in the range of 0.5 to 5 wt%, and when the amount of carbon coating is less than 0.5 wt%, the conductivity of the lithium replenishing agent is lowered, and when the positive electrode lithium replenishing material is added to the positive electrode slurry, the ratio of combustible gas is not increased due to the increase in the amount of lithium replenishing gas, and when the amount of carbon coating is more than 5 wt%, the effect on gas generation is not great, but the lithium replenishing efficiency of the material is lowered.
(4) As can be seen from comparison of examples 9 to 11 with example 1, when Al is present2O3With Li5Fe1-xMnxO4When the molar ratio of (a) is not in the range of 0.01 to 0.1, the viscosity of the positive electrode lithium supplement material added to the positive electrode slurry increases and the gas production rate increases when the alumina ratio is less than 0.01, the combustible gas ratio increases, the explosion limit is exceeded, the safety performance decreases, and when the alumina ratio is greater than 0.1, the viscosity and the combustible gas increase are insignificant, but the lithium supplement efficiency of the lithium supplement agent decreases, preferably 0.01 to 0.04.
(5) As is clear from comparison between example 12 and example 1, when the aluminum sol is not doped with carbon, the viscosity of the positive electrode lithium supplement material added to the positive electrode slurry does not change much, but the conductivity of the lithium supplement agent is reduced, so that the gas yield of combustible gas is increased, and the safety performance is lowered.
(6) As can be seen from comparison between examples 13 and 14 and example 1, when the sintering is not performed stepwise in step (2), the viscosity of the positive electrode lithium supplement material added to the positive electrode slurry does not change much, the gas production rate and the combustible gas ratio increase, and the safety performance decreases.
(7) As can be seen from comparison between comparative example 1 and example 1, when no doped metal is added, the viscosity of the positive electrode lithium supplement material added into the positive electrode slurry is unchanged, the gas production is increased by 10 times, the proportion of combustible gas is increased to be more than 70%, and the safety performance is extremely low.
(8) As is clear from comparison between comparative example 2 and example 1, when no coating is applied, the positive electrode lithium supplement material added to the positive electrode slurry increases in viscosity, forms a gel, and cannot be applied to produce a battery.
(9) As can be seen from comparison between comparative example 3 and example 1, when Ni is used as the replacement of Fe, the viscosity of the positive electrode lithium supplement material added to the positive electrode slurry is not changed, the gas production rate is increased, the proportion of combustible gas is increased, the safety limit is exceeded, and the safety performance is extremely low.
In conclusion, the preparation method of the cathode lithium supplement material provided by the invention obtains the cathode lithium supplement material with an inner doping and outer cladding structure; the modification is carried out by doping metal, so that the problem of high gas generation ratio when lithium ferrite is used as a positive electrode lithium supplement agent is solved; the surface of the lithium supplement agent active material is coated with the alumina coating layer, so that the residual alkali quantity on the surface of the material is reduced, and the agglomeration in the anode slurry is avoided, so that the safety of the lithium ion battery is influenced; in the preparation method, the carbonaceous aluminium sol is used for coating the surface of the lithium ferrite doped with metal; the 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 iron oxide with moisture and carbon dioxide in the air is alkaline is solved, and the gelation of the anode slurry is avoided.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned process, i.e. it does not mean that the present invention must rely on the above-mentioned process. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a positive electrode lithium supplement material is characterized by comprising 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) and (3) mixing the aluminum sol with the LFMO precursor obtained in the step (1), and calcining to obtain the positive electrode lithium supplement material.
2. The method of 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 ≦ 0.01, preferably 0.002 < x ≦ 0.01;
preferably, the concentration of the lithium source in the solution in the step (1) is 0.5-2 mol/L;
preferably, the lithium source of step (1) comprises any one of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate or lithium oxide or a combination of at least two thereof;
preferably, the iron source in step (1) comprises any one of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate or ferric citrate or a combination of at least two of the same;
preferably, the doping metal in step (1) comprises any one or a combination of at least two of Al, Nb, Co, Mn, Ni, Mo, Ru or Cr;
preferably, the doping metal source of step (1) comprises any one of or a combination of at least two of chloride, sulfate or nitrate salts of the doping metal.
3. The method according to claim 1 or 2, wherein the heating time in step (1) is 10 to 60 min;
preferably, the temperature of the heating in the step (1) is 45-98 ℃;
preferably, the drying method of step (1) comprises spray drying;
preferably, the sintering of step (1) comprises a first sintering and a second sintering which are sequentially carried out;
preferably, the first sintering atmosphere comprises an air atmosphere;
preferably, the time of the first sintering is 3-10 h;
preferably, the temperature of the first sintering is 500-700 ℃;
preferably, the second sintering atmosphere comprises a protective gas atmosphere;
preferably, the protective gas comprises nitrogen and/or an inert gas;
preferably, the time of the second sintering is 5-10 h;
preferably, the temperature of the second sintering is 700-.
4. The production method according to any one of claims 1 to 3, wherein the aluminum sol of step (2) comprises AlOOH;
preferably, the aluminum sol contains a carbon source;
preferably, the mass ratio of the AlOOH to the carbon source is (9-12): 1.
5. The method according to any one of claims 1 to 4, wherein the aluminum sol of step (2) is prepared by the following method:
(i) mixing ammonia water and aluminum salt to obtain a solution containing precipitate;
(ii) (ii) mixing an organic acid, a carbon source and the solution containing the precipitate obtained in step (i) to obtain the aluminum sol;
preferably, the liquid-solid ratio of the ammonia water and the aluminum salt in the step (i) is (3-6): 1;
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;
preferably, the mass of the organic acid of step (ii) is 0.01-2 wt% of the solution containing the precipitate;
preferably, the mass of the carbon source in step (ii) is 0.1-0.5 wt% of the solution containing the precipitate.
6. The production method according to any one of claims 1 to 5, wherein the molar ratio of the alumina sol of step (2) to the LFMO precursor of step (1) is 0.01 to 0.1;
preferably, the calcination of step (2) is carried out in a protective gas atmosphere;
preferably, the protective gas comprises nitrogen and/or an inert gas;
preferably, the temperature of the calcination in the step (2) is 450-600 ℃;
preferably, the calcination time of the step (2) is 2-10 h.
7. The production method according to any one of claims 1 to 6, characterized by comprising 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 carried out in an air atmosphere for 3-10h at the temperature of 500-900 ℃, the second sintering is carried out in an inert gas atmosphere for 5-10h at the temperature of 700-900 ℃;
the molar ratio of the lithium source, the iron source and the doped metal source in the solution is Li, Fe, M is 5 (1-x) x, wherein x is more than 0 and less than or equal to 0.01;
(2) mixing the aluminum sol with the LFMO precursor obtained in the step (1) according to a molar ratio of 0.01-0.1, and calcining for 2-10h in a nitrogen and/or inert atmosphere at the calcining temperature of 450-600 ℃ to obtain the anode lithium supplement material;
the preparation method of the aluminum sol comprises the following steps:
(i) ammonia water and aluminum salt with the mixed liquid-solid ratio of (3-6) to 1 to obtain a solution containing precipitates;
(ii) (ii) mixing citric acid, an organic carbon source and the solution containing the precipitate obtained in step (i) to obtain the aluminum sol;
the organic carbon source comprises any one or the 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 0.01-2 wt% of the solution containing the precipitate;
the mass of the organic carbon source is 0.1-0.5 wt% of the solution containing the precipitate.
8. A positive electrode lithium supplement material obtained by the production method according to any one of claims 1 to 7.
9. The positive lithium supplement material according to claim 8, wherein the positive lithium supplement material comprises an active material and a surface coating;
preferably, the active material has a chemical formula of Li5Fe1-xMxO4Wherein x is more than 0 and less than or equal to 0.01, and M comprises any one or the combination of at least two of Al, Nb, Co, Mn, Ni, Mo, Ru or Cr;
preferably, the positive electrode lithium supplement material has a particle size D50≤3μm；
Preferably, the surface coating comprises Al2O3；
Preferably, in the positive electrode lithium supplement material, Al2O3With Li5Fe1-xMxO4In a molar ratio of from 0.005 to 0.05, preferably from 0.005 to 0.02;
preferably, the surface coating further comprises carbon;
preferably, the mass of the carbon is 0.2-5 wt%, preferably 0.2-3.5 wt% of the positive electrode lithium supplement material.
10. A lithium ion battery comprising the positive electrode lithium supplement material according to claim 8 or 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115676895A (en) * | 2022-11-09 | 2023-02-03 | 山东海科创新研究院有限公司 | Lithium-rich lithium iron oxide and synthesis method thereof |
| CN115863913A (en) * | 2022-12-28 | 2023-03-28 | 重庆太蓝新能源有限公司 | Preparation method of lithium-supplement diaphragm, diaphragm and lithium ion battery |
| CN116230842A (en) * | 2022-12-12 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium supplementing agent |
| CN117154003A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, preparation method, sodium secondary battery and power utilization device |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180026317A1 (en) * | 2016-07-19 | 2018-01-25 | Uchicago Argonne, Llc | PHOTO-ASSISTED FAST CHARGING OF LITHIUM MANGANESE OXIDE SPINEL (LiMn2O4) IN LITHIUM-ION BATTERIES |
| CN107740143A (en) * | 2017-09-29 | 2018-02-27 | 武汉大学 | A kind of iron-based inert anode with ferrous acid lithium diaphragm and preparation method thereof, application |
| CN108878849A (en) * | 2018-07-04 | 2018-11-23 | 江西中汽瑞华新能源科技有限公司 | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium |
| CN109585839A (en) * | 2019-01-16 | 2019-04-05 | 合肥国轩高科动力能源有限公司 | A kind of alumina-coated nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN110299496A (en) * | 2018-03-23 | 2019-10-01 | 比亚迪股份有限公司 | A kind of battery diaphragm, power battery and vehicle |
| CN112054181A (en) * | 2020-09-28 | 2020-12-08 | 珠海冠宇电池股份有限公司 | Lithium supplement agent and application thereof |
| CN112186143A (en) * | 2020-08-14 | 2021-01-05 | 安徽德亚电池有限公司 | Modified lithium iron oxide positive electrode material, preparation method thereof and positive plate |
| CN112490415A (en) * | 2019-09-12 | 2021-03-12 | 湖南杉杉能源科技股份有限公司 | Lithium ion anode material lithium supplement additive and preparation method thereof |
| WO2022042665A1 (en) * | 2020-08-27 | 2022-03-03 | 比亚迪股份有限公司 | Electrode plate and lithium ion battery |
| CN114242939A (en) * | 2021-12-20 | 2022-03-25 | 惠州亿纬锂能股份有限公司 | Modified positive electrode lithium supplement material and preparation method and application thereof |
-
2022
- 2022-04-01 CN CN202210347811.3A patent/CN114709391B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180026317A1 (en) * | 2016-07-19 | 2018-01-25 | Uchicago Argonne, Llc | PHOTO-ASSISTED FAST CHARGING OF LITHIUM MANGANESE OXIDE SPINEL (LiMn2O4) IN LITHIUM-ION BATTERIES |
| CN107740143A (en) * | 2017-09-29 | 2018-02-27 | 武汉大学 | A kind of iron-based inert anode with ferrous acid lithium diaphragm and preparation method thereof, application |
| CN110299496A (en) * | 2018-03-23 | 2019-10-01 | 比亚迪股份有限公司 | A kind of battery diaphragm, power battery and vehicle |
| CN108878849A (en) * | 2018-07-04 | 2018-11-23 | 江西中汽瑞华新能源科技有限公司 | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium |
| CN109585839A (en) * | 2019-01-16 | 2019-04-05 | 合肥国轩高科动力能源有限公司 | A kind of alumina-coated nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN112490415A (en) * | 2019-09-12 | 2021-03-12 | 湖南杉杉能源科技股份有限公司 | Lithium ion anode material lithium supplement additive and preparation method thereof |
| CN112186143A (en) * | 2020-08-14 | 2021-01-05 | 安徽德亚电池有限公司 | Modified lithium iron oxide positive electrode material, preparation method thereof and positive plate |
| WO2022042665A1 (en) * | 2020-08-27 | 2022-03-03 | 比亚迪股份有限公司 | Electrode plate and lithium ion battery |
| CN112054181A (en) * | 2020-09-28 | 2020-12-08 | 珠海冠宇电池股份有限公司 | Lithium supplement agent and application thereof |
| CN114242939A (en) * | 2021-12-20 | 2022-03-25 | 惠州亿纬锂能股份有限公司 | Modified positive electrode lithium supplement material and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115676895A (en) * | 2022-11-09 | 2023-02-03 | 山东海科创新研究院有限公司 | Lithium-rich lithium iron oxide and synthesis method thereof |
| CN116230842A (en) * | 2022-12-12 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium supplementing agent |
| CN116230842B (en) * | 2022-12-12 | 2024-04-02 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium supplementing agent |
| CN115863913A (en) * | 2022-12-28 | 2023-03-28 | 重庆太蓝新能源有限公司 | Preparation method of lithium-supplement diaphragm, diaphragm and lithium ion battery |
| CN115863913B (en) * | 2022-12-28 | 2024-03-22 | 重庆太蓝新能源有限公司 | Preparation method of lithium supplementing diaphragm, diaphragm and lithium ion battery |
| CN117154003A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, preparation method, sodium secondary battery and power utilization device |
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