CN109244366A - A kind of richness surface recombination modified method of the lithium material and its rich lithium material of preparation - Google Patents
A kind of richness surface recombination modified method of the lithium material and its rich lithium material of preparation Download PDFInfo
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- CN109244366A CN109244366A CN201811426400.3A CN201811426400A CN109244366A CN 109244366 A CN109244366 A CN 109244366A CN 201811426400 A CN201811426400 A CN 201811426400A CN 109244366 A CN109244366 A CN 109244366A
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- lithium material
- rich lithium
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- surface recombination
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- 239000000463 material Substances 0.000 title claims abstract description 171
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 126
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 83
- 238000005215 recombination Methods 0.000 title claims abstract description 29
- 230000006798 recombination Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 15
- 230000004913 activation Effects 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 28
- 239000011572 manganese Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000001994 activation Methods 0.000 description 12
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 11
- 238000005253 cladding Methods 0.000 description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 description 9
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010792 warming 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
-
- 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
- H01M4/36—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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 belongs to technical field of lithium ion, and in particular to a kind of surface recombination modified method of richness lithium material, and the rich lithium material of this method preparation is further disclosed, and its prepares the purposes of anode material for lithium-ion batteries.The surface recombination modified method of richness lithium material of the present invention can complete the coating modification to material while carrying out chemical activation to rich lithium material.The method of the invention carries out the modified rich lithium material in surface, and compared with single chemical pre-activate or surface coating modification, capacity when coulombic efficiency, high rate performance and circulation and voltage retention are obviously improved for the first time.In addition, this composite modifying method has stronger applicability and relatively simple process flow, it is suitble to large-scale industrialization application.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of surface recombination modified method of richness lithium material,
And the rich lithium material of this method preparation is further disclosed, and its prepare the purposes of anode material for lithium-ion batteries.
Background technique
Lithium ion battery has been widely used in since commercialization as a kind of efficient energy conversion and storage facilities
Every field.Especially in recent years, with the rapid development of new-energy automobile industry, people are as new-energy automobile power resources
Lithium ion battery more stringent requirements are proposed.In lithium ion battery, lithium ion anode material as influence and restrict lithium from
The principal element of sub- battery energy density receives more concerns naturally.In numerous positive electrodes, there is high capacity, low
The rich lithium material of the features such as cost, hypotoxicity becomes research hotspot, and holds promise as positive electrode applied to follow-on
In high specific energy lithium ion battery.However, it is this richness lithium material there is some intrinsic short slabs, for example, have it is biggish for the first time
The defects of operating voltage when irreversible capacity, poor high rate performance and circulation decays, these performance short slabs make rich lithium
Material is restricted applied to lithium ion anode material.
Studies have shown that the disadvantages mentioned above of rich lithium material mostlys come from the Li in material2MnO3Component, although Li2MnO3Group
The activation energy divided is the next additional capacity of material strips, but usually in initial charge, Li2MnO3The activation of component often can be along with O
Irreversible oxidation and oxygen precipitation, and the Li thus caused+Irreversible deintercalation be cause the material for the first time coulombic efficiency compared with
The main reason for low；Moreover, the Li after activation2MnO3Component can constantly turn to spinel-like structural in subsequent cyclic process
Become, this also results in the lasting reduction of its operating voltage；And Li2MnO3Mutually lower conductivity and ion conductance are also unfavorable for material
The high rate performance of material.These cause serious restriction to the performance of rich lithium material to a certain extent.
In order to overcome disadvantage mentioned above, it usually needs be further modified to rich lithium material.Due to during the charging process
Many unfavorable problems (electricity in such as lower coulombic efficiency for the first time, cyclic process can be caused to the electrochemical activation of rich lithium material
Pressure and capacity attenuation etc.), therefore, material is carried out to chemical activation it is proved to be a kind of improving the effective of rich lithium material performance in advance
Means.Wherein, acid processing be a kind of common chemical pre-activate richness lithium material method (J.Electrochem.Soc 2006,
153,A1186-A1192).H can be ionized out when material is scattered in+Aqueous solution in when, the Li in material surface+It can be by H+Institute
Displacement, and the spinel structure that can be formed in subsequent heat treatment process conducive to lithium ion transport.But it is activated in this liquid phase
In the process, many factors (such as temperature, time, the pH value even mixing speed when handling) can all influence Li+Replacement amount, go forward side by side
And the structure and performance of final product are influenced, this is very unfavorable for keeping the consistency of modified material.And another
In the chemical pre-activation method of kind, ammonium sulfate is mixed and is heat-treated with rich lithium material, so that the Li of material surface+Abjection is simultaneously
Li is formed in conjunction with ammonium sulfate2SO4, then by readily soluble Li2SO4It washes off and is equally reached to the preactivated effect of rich lithium material
Fruit (J.Electrochem.Soc 2010,157, A1177-A1182).In this solid phase activation process, due to Li+Abjection amount
It is only determined by the dosage of ammonium sulfate, therefore is easier to obtain the consistent modified material of performance.It is handled by above-mentioned chemical pre-activate
Rich lithium material afterwards, it turned out that coulombic efficiency and high rate performance can be obviously improved for the first time for it, and voltage when circulation declines
Subtracting can also be inhibited.But active material and electrolyte when not can be reduced charge and discharge during above-mentioned chemical pre-activate
Between side reaction, so the capacity in cyclic process that above-mentioned method of modifying can not be obviously improved rich lithium material declines
Subtract.And surface cladding facilitates to promote the method for modifying of material property as another kind, although active material can be effectively reduced
Side reaction between material and electrolyte, and capacity retention ratio of the material in circulation is promoted in turn, but only abutment surface coats not
It can be obviously improved the inherent defect of rich lithium material, voltage attenuation when such as aforementioned lower coulombic efficiency for the first time and circulation is asked
Topic.
It can be seen that only by the chemical pre-activate of rich lithium material or surface cladding can not improvement in all directions its
Intrinsic disadvantage.It therefore, is considered as that can integrate the rich lithium material electrochemistry of raising in conjunction with the surrounding phase of surface by chemical activation
Effective modified method of performance.Such as Chinese patent CN102738458A and document (Electrochim.Acta, 2015,163,
82-92) disclosed in, rich lithium material is first subjected to pre-activate and then surface cladding is carried out to it, and then reaches comprehensive promotion
The effect of material electrochemical performance；But in this processing method, the pre-activate of material and surface cladding are individual with two
What step separately carried out, therefore cause process flow complex.And one kind one is disclosed in Chinese patent CN103441240A
The method that footwork prepares surface cladding and chemical activation richness lithium solid solution cathode material, this method utilize the alcoholic solution pair of nitrate
Rich lithium material is handled, so that treated, rich lithium material surface has coated one layer of inert metal oxide, and changes simultaneously
Abjection part lithium ion is learned, the comprehensive electrochemical of rich lithium material after the processing of the method is significantly improved.However, this
Chemical lithium deintercalation is completed in the liquid phase in method, and the abjection of lithium ion is caused to be influenced by more factor, and is unfavorable for controlling
The abjection amount of preparing lithium ion, and the consistency of modified material is influenced in turn；Moreover, because the cladding process in the method is in liquid
It is carried out in phase, is also not particularly suited for coating the salt of certain indissolubles.
Therefore, it is necessary to develop a kind of controllability and the stronger comprehensive modification method of applicability, make it possible to show simultaneously
The multiplying power for promoting rich lithium material, cycle performance and coulombic efficiency for the first time are write, and has stronger versatility and simple technique
Process can be suitable for large-scale industrial production, have very positive industrial significance.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in a kind of surface recombination modified method of rich lithium material is provided,
The above method can make rich lithium material in such a way that solid phase takes off lithium by pre-activate, and be completed at the same time the surface cladding to material, from
And achieve the purpose that General Promotion coulombic efficiency, high rate performance and cycle performance for the first time；
The invention also discloses the above-mentioned rich lithium materials being prepared by surface recombination modified method, and further disclose
Above-mentioned richness lithium material is used to prepare the purposes of anode material for lithium-ion batteries.
In order to solve the above technical problems, a kind of surface recombination modified method of rich lithium material of the present invention, feature
It is, includes the following steps:
(1) rich lithium material is taken to carry out pre-coated processing, by sulfur-containing compound and pre-coated object simultaneously pre-coated selected
Rich lithium material surface；
(2) under an oxygen-containing atmosphere by the rich lithium material after above-mentioned pre-coated, it is heat-treated in 150-850 DEG C, obtains powder
Body；
(3) powder after above-mentioned heat treatment through washing, filtering and is dried, obtains the modified rich lithium material in surface.
In the step (1), it is Li that the richness lithium material, which includes structural formula,1+xMnyMzAwOrRich lithium compound；Wherein,
The M element includes at least one of Ni, Co, A1, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru or Sn element；
The element A includes at least one of S, P, B or F element；
And the parameter x, y, z, w and r meet following condition: 0 < x≤1,0 < y≤1,0≤z < 1,0≤w≤0.2,
1.8≤r≤3。
In the step (1), the quality of the sulfur-containing compound accounts for the 1-40wt% of the rich lithium material quality；It is described pre-
The quality of coating accounts for the 0.1-10wt% of the rich lithium material quality.
In the step (1), the sulfur-containing compound includes ammonium sulfate, ammonium hydrogen sulfate, ATS (Ammonium thiosulphate), persulfuric acid
At least one of ammonium, sodium thiosulfate, sodium peroxydisulfate, potassium thiosulfate or potassium peroxydisulfate.
In the step (1), the pre-coated object includes metallic compound or ammonium phosphate salt；
The metallic compound includes in Mg, Al, Sn, Ti, V, Cr, Mn, Ni, Co, Fe, Cu, Zn, Zr, Nb, Mo or W
The corresponding oxide of at least one metal, carbonate, nitrate, phosphate, sulfate or acylate；
The ammonium phosphate salt includes at least one of ammonium phosphate, ammonium hydrogen phosphate or diammonium hydrogen phosphate.
In the step (1), the pre-coated processing step includes solid phase method or liquid phase method.The solid phase method or liquid phase method
It is method in the prior art.
The liquid phase method may include: first by soluble pre-coated object and sulfur-containing compound be dissolved in simultaneously water, ethyl alcohol or
The mixture of person's water and ethyl alcohol by a certain percentage, then in the above solution by the dispersion of rich lithium material, under agitation, maintain body
It is temperature at 60-100 DEG C, until solvent is evaporated.
The solid phase method may include two kinds of feasible methods, and one specifically includes: by sulfur-containing compound, pre-coated
Object, rich lithium material and appropriate solvent are added to ball mill and carry out ball milling mixing, drum's speed of rotation 200-800r/min, when ball milling
Between be 2-20h, ball material weight ratio be 3-20:1；Secondly specifically including: sulfur-containing compound, pre-coated object, rich lithium material are added
High-speed stirred mixing is carried out into high speed mixer, control high speed mixer revolving speed is 500-10000r/min, when being mixed
Between be 1-20h.
Selection for the pre-coated method, as pre-coated object be it is soluble if may be selected liquid phase method, such as it is insoluble, then
Solid phase method may be selected.
In the step (2), the oxygen-containing atmosphere includes gas of the air or oxygen with nitrogen to mix under certain proportion.
In the step (2), the processing time of the heat treatment step is preferably 10min-20h.
In the step (3), the temperature for controlling the drying steps is 80-300 DEG C, and the time of the drying steps is
10min-20h。
The invention also discloses the modified rich lithium materials in the surface as made from the surface recombination modified method.
The invention also discloses a kind of lithium ion cell positives, are made by the rich lithium material.Specifically, selecting this hair
The modified rich lithium material in the bright obtained surface of method is uniformly mixed with conductive agent, binder, is dissolved in organic solvent, is formed
Anode sizing agent is coated on supporter, the anode of lithium ion battery is made.
The invention also discloses a kind of lithium ion batteries, including the lithium ion cell positive.Specifically, selecting this hair
The bright lithium ion cell positive, and the electric compatible cathode of rich lithium material for select surface obtained with the present invention modified as
Diaphragm, electrolyte is added in the cathode of lithium ion battery, forms lithium ion battery.
The surface recombination modified method of richness lithium material of the present invention can carry out chemical activation to rich lithium material
Meanwhile coating modification of the completion to material.In the method for the invention, first sulfur-containing compound and pre-coated object are coated on simultaneously
Rich lithium material surface, in subsequent heat treatment process: the Li in material surface+Solid phase reaction shape can occur with sulfur-containing compound
At Li2SO4, and pre-coated object can then be converted into metal oxide or lithium phosphate cladding on the surface of the material.Powder after heat treatment
After being washed, being filtered, readily soluble Li2SO4It can be washed away with other sulfate, and the metal oxide of indissoluble or lithium phosphate then stay
Covered effect is played on the surface of the material.After above-mentioned processing, the pre- de- lithium effect meeting of sulfur-containing compound is so that in rich lithium material
Li2MnO3Component substantially reduces, and will form the spinel structure for being conducive to lithium ion transport in material surface, therefore material
Voltage retention when coulombic efficiency for the first time, high rate performance and the circulation expected is obviously improved；And stay in the packet of material surface
Covering object helps to reduce the side reaction between electrode and electrolyte, and then plays the role of inhibiting capacity attenuation in cyclic process.
The method of the invention carries out the modified rich lithium material in surface, compared with single chemical pre-activate or surface coating modification,
Enough comprehensive every chemical properties for promoting rich lithium material, including coulombic efficiency for the first time, high rate performance and cycle performance.
In surface recombination modified method of the present invention, the activation step (i.e. pre- de- lithium) of rich lithium material is anti-with solid phase
What the mode answered was completed, compared with the modification scheme that the rich lithium material in liquid phase activates and coats, it is more convenient for controlling lithium ion
Quantitative abjection, and then be conducive in obtaining the consistent modified material of performance；Meanwhile it can also benefit for the pre-coated object of some indissolubles
It is coated with solid phase method, therefore its applicability is wider.Also, the method for modifying in the present invention only needs a pre-coated and Re Chu
Manage step, more simple, suitable large-scale industrial production in process flow.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is X-ray diffraction (XRD) map of material prepared in embodiment 1 and comparative example 1-3；
Fig. 2 is scanning electron microscope (SEM) figure of comparative example 1 (A in Fig. 1), material prepared in embodiment 1 (B in Fig. 1)；
Fig. 3 is the EDS distribution diagram of element of material prepared in embodiment 1；
Fig. 4 is discharge capacity comparison of the material prepared in embodiment 1 and comparative example 1-3 under different current densities
Figure；
Fig. 5 is discharge capacity comparison of the material prepared in embodiment 1 and comparative example 1-3 under different circulating cycle numbers
Figure；
Fig. 6 is that material prepared in embodiment 1 and comparative example 1-3 presses comparison in the electric discharge under different circulating cycle numbers
Figure.
Specific embodiment
Embodiment 1
It is structural formula Li that surface recombination modified method described in the present embodiment, which carries out the modified rich lithium material in surface,
[Li0.12Ni0.32Co0.07Mn0.5]O2Material, specific preparation step includes:
Nickel protoxide, oxidation are weighed according to the ratio (Li:Ni:Co:Mn=1.12:0.32:0.07:0.5) of the amount of substance
Cobalt, manganese dioxide and lithium carbonate, wherein lithium carbonate excessive 4%, after being mixed 8 hours in batch mixer, by solid content 20wt%'s
Deionized water is added in ratio, then pours into ball mill slurry and is ground to middle granularity less than 0.3 micron；The slurry that will finally obtain
Material is spray-dried to arrive Li [Li0.12Ni0.3Co0.06Mn0.5]O2Presoma；
Presoma is kept the temperature 5 hours at 450 DEG C, then proceedes to be warming up to 950 DEG C, keeps the temperature 20 hours；Last Temperature fall
To room temperature to get arrive Li [Li0.12Ni0.32Co0.07Mn0.5]O2Material.
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) weigh 10g ammonium sulfate, 2g diammonium hydrogen phosphate is dissolved in 100ml water, by 100g group become Li
[Li0.12Ni0.32Co0.07Mn0.5]O2Rich lithium material be scattered in the solution, and stirring is evaporated to solution at 80 DEG C；
(2) then by dry powder in air atmosphere, carry out heat treatment 4h, furnace cooling in 750 DEG C；
(3) powder after above-mentioned heat treatment washed with deionized water, filtered, and carry out drying 2h at 300 DEG C, most
Surface recombination modified rich lithium material is obtained eventually.
Comparative example 1
Richness lithium material described in this comparative example is that structural formula obtained is Li [Li in embodiment 10.12Ni0.32Co0.07Mn0.5]O2
Rich lithium material, do not carry out surface modification treatment.
Comparative example 2
Rich lithium material described in this comparative example carries out surface recombination modified method, for using ammonium sulfate to rich lithium material into
The method of modifying of row surface active comprising following steps: it weighs 10g ammonium sulfate and is dissolved in 100ml water, 100g group is become
Li[Li0.12Ni0.32Co0.07Mn0.5]O2Rich lithium material be scattered in the solution, and stirring is evaporated to solution at 80 DEG C；With
Afterwards by dry powder in 750 DEG C of heat treatment 4h, furnace cooling, by the powder after heat treatment to wash, filter in deionized water,
And in 300 DEG C of drying 2h, the rich lithium material of surface active is finally obtained.
Comparative example 3
Rich lithium material described in this comparative example carries out surface recombination modified method, to carry out surface cladding to rich lithium material
The method of modifying of lithium phosphate comprising following steps: it weighs 2g diammonium hydrogen phosphate and is dissolved in 100ml water, 100g group is become
Li[Li0.12Ni0.32Co0.07Mn0.5]O2Rich lithium material be scattered in the solution, and stirring is evaporated to solution at 80 DEG C；With
Afterwards by dry powder in 750 DEG C of heat treatment 4h, furnace cooling finally obtains the rich lithium material of surface cladding lithium phosphate.
Its performance test is carried out to the rich lithium material in above-described embodiment 1 and comparative example 1-3.
Fig. 1 is the X ray diffracting spectrum of richness lithium material described in embodiment 1 and comparative example 1-3, it can be seen from the figure that
Layer structure is still maintained through the modified material in the method for the present invention surface.In comparative example 2 and embodiment 1,20-25 ° super
The decrease of lattice diffraction maximum, this corresponds to Li in rich lithium material2MnO3The reduction of component, illustrates through the pre- of ammonium persulfate
Part Li after activation in material+Deviate from；In addition, do not find the diffraction maximum of lithium sulfate in comparative example 2 and embodiment 1,
Illustrate that lithium sulfate is washed away；And there is very weak lithium phosphate diffraction maximums in comparative example 3 and embodiment 1, illustrate lithium phosphate
Still it is coated on rich lithium material surface.
As can be seen that surface made from composite modifying method of the present invention is modified from scanning electron microscope (SEM) photograph shown in Fig. 2
Rich lithium material (B in Fig. 2) relative to untreated rich lithium material (A in Fig. 2), the pattern and partial size of material obviously do not become
Change.
It can be seen that, the P element in embodiment 1 is uniformly distributed in rich lithium material from EDS distribution diagram of element shown in Fig. 3
Surface.
ICP in the following table 1 is the results show that the content Yu comparative example 3 of material P are very close in embodiment 1, and embodiment 1
The content of middle P is much higher than the content of S, this further illustrates the greatest differences due to solubility, washes away in embodiment 1 readily soluble
While lithium sulfate, the lithium phosphate of indissoluble remains in material surface.
Table 1 by the ICP embodiment 1 measured and comparative example 1-3 material prepared elemental mole ratios
| Ni | Co | Mn | Li | P | S | |
| Embodiment 1 | 0.570 | 0.360 | 0.076 | 1.140 | 0.014 | 0.002 |
| Comparative example 1 | 0.570 | 0.362 | 0.077 | 1.300 | 0 | 0 |
| Comparative example 2 | 0.570 | 0.360 | 0.077 | 1.150 | 0 | 0.002 |
| Comparative example 3 | 0.570 | 0.359 | 0.076 | 1.290 | 0.015 | 0 |
The rich lithium material prepared respectively using in above-described embodiment 1 and comparative example 1-3 is as positive electrode, using lithium piece as negative
Pole material, is assembled into button cell, and constant current charge-discharge test, the voltage range of charge and discharge are as follows: 2- are carried out under the conditions of 25 DEG C
4.8V, and the current density for defining 200mA/g is 1C.
Electric discharge of the material prepared in embodiment 1 and comparative example 1-3 under different current densities is set forth in Fig. 4-6
Capacity comparison figure, the discharge capacity comparison diagram under different circulating cycle numbers and in the electric discharge under different circulating cycle numbers pressure pair
Than figure, table 2 gives the electrochemical property test tables of data of material prepared in embodiment 1 and comparative example 1-3.
The electrochemical property test tables of data of material prepared by 2 embodiment 1 of table and comparative example 1-3
It can see from Fig. 4-6 and table 2, it is first individually through the preactivated rich lithium material of ammonium persulfate in comparative example 2
Voltage retention when secondary coulombic efficiency, high rate performance and 1C are recycled is promoted obviously, but capacity retention ratio when 1C circulation does not have
Improve；In comparative example 3, the rich lithium material of lithium phosphate is individually coated, capacity retention ratio when 1C is recycled is obviously improved, but other
The improvement of chemical property is unobvious；And in embodiment 1, every chemical property of material obtains compared with comparative example 1
It is obviously improved.
It can be seen that in embodiment 1, the pre-activate that rich lithium material not only passes through ammonium sulfate greatly improves coulomb for the first time
Efficiency and high rate performance, and since the lithium phosphate of electrochemicaUy inert is present in material surface, reduce active material and is being electrolysed
Exposed area in liquid, so that the cycle performance of material further gets a promotion.
To sum up, the composite modifying method of the present invention to rich lithium material surface, can significantly improve material circulation,
High rate performance and for the first time coulombic efficiency, and process flow is simple, is suitble to large-scale production.
Embodiment 2
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) 6g Al (NO is weighed3)3·9H2O, 20g (NH4)2S2O8It is dissolved in 100ml water, 100g group is become into Li
[Li0.20Ni0.13Co0.13Mn0.54]O2The rich lithium material of (being made by art methods) is scattered in the solution, and at 80 DEG C
Stirring to solution is evaporated；
(2) then by said mixture in 550 DEG C of heat treatment 5h, furnace cooling；
(3) it by the powder after above-mentioned heat treatment to wash, filter in deionized water, and in 300 DEG C of drying 1h, finally obtains
The rich lithium material of surface active and coated aluminum oxide.
Embodiment 3
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) by 5ml Mn (NO3)2Solution, 6g Na2S2O8It is dissolved in 15ml water, 10g group is become into Li
[Li0.20Ni0.20Mn0.60]O2The rich lithium material of (being made by art methods) is scattered in the solution, and is stirred at 80 DEG C
It is evaporated to solution；
(2) then by said mixture in 750 DEG C of heat treatment 4h, furnace cooling；
(3) by the powder after heat treatment to wash, filter in deionized water, and in 150 DEG C of drying 5h, surface is finally obtained
Activate the rich lithium material of simultaneously coating spinelle LiMn2O4.
Embodiment 4
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) 20g nanoscale ZrO is weighed2, 150g (NH4)2SO4Become Li [Li with 900g group0.20Ni0.20Mn0.60]O2(by existing
Have technical method be made) rich lithium material be placed in high speed mixer, carry out mixed at high speed, revolving speed 8000r/min, incorporation time
3h；
(2) then by said mixture in 700 DEG C of heat treatment 4h, furnace cooling；
(3) by the powder after heat treatment to wash, filter in deionized water, and in 300 DEG C of drying 1h, surface is finally obtained
Activate and coat the rich lithium material of lithium zirconate.
Embodiment 5
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) 0.2g MgO, 3.5g Na are weighed2S2O3, 10g group is as Li [Li0.20Ni0.20Mn0.60]O2(press the prior art
Method be made) rich lithium material be placed in ball mill, carry out ball milling mixing, revolving speed 800r/min, Ball-milling Time 6h；
(2) then by said mixture in 600 DEG C of heat treatment 10h, furnace cooling；
(3) by the powder after heat treatment to wash, filter in deionized water, and in 200 DEG C of drying 3h, surface is finally obtained
Activate the rich lithium material of simultaneously coated magnesium oxide.
Embodiment 6
Rich lithium material described in the present embodiment carries out surface recombination modified method, includes the following steps:
(1) 0.4g Mn (CH is weighed3COO)2·4H2O,0.2g Al(NO3)3·9H2O, 1g (NH4)2SO4It is dissolved in 20ml
In water, 10g group is become into Li [Li0.20Ni0.13Co0.13Mn0.54]O2The rich lithium material of (being made by art methods) is scattered in
In the solution, and stirring to solution is evaporated at 80 DEG C；
(2) then by said mixture in 650 DEG C of heat treatment 5h, furnace cooling；
(3) by the powder after heat treatment to wash, filter in deionized water, and in 300 DEG C of drying 2h, surface is finally obtained
Activate and be total to the rich lithium material of coated aluminum oxide and spinel lithium manganate.
Electrochemical property test is carried out to the modified rich lithium material in surface made from above-described embodiment 2-6, test result is shown in
The following table 3.
The electrochemical property test tables of data of prepared material in 3 embodiment 2-6 of table
From upper table data it is found that the composite modifying method of the present invention to rich lithium material surface, can significantly improve
The circulation of material, high rate performance and coulombic efficiency for the first time, and process flow is simple, is suitble to large-scale production.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of surface recombination modified method of richness lithium material, which comprises the steps of:
(1) rich lithium material is taken to carry out pre-coated processing, by sulfur-containing compound and pre-coated object simultaneously pre-coated in selected rich lithium
Material surface；
(2) under an oxygen-containing atmosphere by the rich lithium material after above-mentioned pre-coated, it is heat-treated in 150-850 DEG C, obtains powder；
(3) powder after above-mentioned heat treatment through washing, filtering and is dried, obtains the modified rich lithium material in surface.
2. the surface recombination modified method of richness lithium material according to claim 1, which is characterized in that in the step (1),
It is Li that the richness lithium material, which includes structural formula,1+xMnyMzAwOrRich lithium compound；Wherein,
The M element includes at least one of Ni, Co, A1, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru or Sn element；
The element A includes at least one of S, P, B or F element；
And the parameter x, y, z, w and r meet following condition: 0 < x≤1,0 < y≤1,0≤z < 1,0≤w≤0.2,1.8≤r
≤3。
3. the surface recombination modified method of richness lithium material according to claim 1 or 2, which is characterized in that the step (1)
In, the quality of the sulfur-containing compound accounts for the 1-40wt% of the rich lithium material quality；The quality of the pre-coated object accounts for described
The 0.1-10wt% of rich lithium material quality.
4. the surface recombination modified method of richness lithium material according to claim 1-3, which is characterized in that the step
Suddenly in (1), the sulfur-containing compound includes ammonium sulfate, ammonium hydrogen sulfate, ATS (Ammonium thiosulphate), ammonium persulfate, sodium thiosulfate, mistake
At least one of sodium sulphate, potassium thiosulfate or potassium peroxydisulfate.
5. the surface recombination modified method of richness lithium material according to claim 1-4, which is characterized in that the step
Suddenly in (1), the pre-coated object includes metallic compound or ammonium phosphate salt；
The metallic compound include in Mg, Al, Sn, Ti, V, Cr, Mn, Ni, Co, Fe, Cu, Zn, Zr, Nb, Mo or W at least
A kind of corresponding oxide of metal, carbonate, nitrate, phosphate, sulfate or acylate；
The ammonium phosphate salt includes at least one of ammonium phosphate, ammonium hydrogen phosphate or diammonium hydrogen phosphate.
6. the surface recombination modified method of richness lithium material according to claim 1-5, which is characterized in that the step
Suddenly in (1), the pre-coated processing step includes solid phase method or liquid phase method.
7. the surface recombination modified method of richness lithium material according to claim 1-6, which is characterized in that the step
Suddenly in (3), the temperature for controlling the drying steps is 80-300 DEG C.
8. the modified rich lithium material in the surface as made from claim 1-7 described in any item surface recombination modified methods.
9. a kind of lithium ion cell positive, which is characterized in that be made by rich lithium material according to any one of claims 8.
10. a kind of lithium ion battery, which is characterized in that including lithium ion cell positive as claimed in claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364703A (en) * | 2019-06-11 | 2019-10-22 | 浙江吉利控股集团有限公司 | A kind of composite material and preparation method thereof, anode, battery and preparation method thereof |
| CN111422920A (en) * | 2019-12-26 | 2020-07-17 | 蜂巢能源科技有限公司 | Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery |
| CN114583120A (en) * | 2021-12-27 | 2022-06-03 | 武汉理工大学 | Method for designing and constructing gradient structure with metal ion component on surface of lithium-rich material |
| CN115286042A (en) * | 2022-09-22 | 2022-11-04 | 河南电池研究院有限公司 | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208607A (en) * | 2011-04-29 | 2011-10-05 | 广州市香港科大***研究院 | Synthesis and surface modification method of lithium excessive laminar oxide anode material |
| CN102738458A (en) * | 2012-06-13 | 2012-10-17 | 北京有色金属研究总院 | Surface modification method of lithium-rich cathode material |
| CN103441240A (en) * | 2013-08-02 | 2013-12-11 | 中国科学院长春应用化学研究所 | Single-step preparation method of surface coating and chemical activation lithium-rich solid solution anode material |
| CN104577101A (en) * | 2014-12-25 | 2015-04-29 | 芜湖市汽车产业技术研究院有限公司 | Preparation method for surface-modified lithium-manganese-rich cathode material of lithium ion battery |
| CN104900860A (en) * | 2014-03-04 | 2015-09-09 | 北京有色金属研究总院 | Lithium-rich positive electrode material surface modification method, positive electrode containing surface-modified lithium-rich positive electrode material, and lithium ion battery |
| WO2016063281A1 (en) * | 2014-10-21 | 2016-04-28 | Ramot At Tel-Aviv University Ltd | High-capacity silicon nanowire based anode for lithium-ion batteries |
| CN106450194A (en) * | 2016-10-13 | 2017-02-22 | 华南师范大学 | Manganese-based lamellar lithium-rich material provided with uniform lithium phosphate coating layer and preparation method thereof |
| CN106602024A (en) * | 2016-12-28 | 2017-04-26 | 国联汽车动力电池研究院有限责任公司 | In-situ surface-modified lithium-rich material and preparation method thereof |
| CN106848227A (en) * | 2017-01-23 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified lithium-rich manganese-based anode material in surface |
| WO2017150915A1 (en) * | 2016-03-04 | 2017-09-08 | 주식회사 엘 앤 에프 | Positive electrode active material for lithium secondary battery, method for producing same and lithium secondary battery comprising same |
| CN108075111A (en) * | 2016-11-18 | 2018-05-25 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and positive electrode material thereof |
| CN108172803A (en) * | 2017-12-30 | 2018-06-15 | 国联汽车动力电池研究院有限责任公司 | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery |
| CN108199024A (en) * | 2017-12-30 | 2018-06-22 | 国联汽车动力电池研究院有限责任公司 | A kind of rich lithium material of surface recombination cladding and preparation method thereof |
| CN108615875A (en) * | 2018-05-04 | 2018-10-02 | 中南大学 | A kind of lithium-rich manganese-based anode material and preparation method thereof |
-
2018
- 2018-11-27 CN CN201811426400.3A patent/CN109244366B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208607A (en) * | 2011-04-29 | 2011-10-05 | 广州市香港科大***研究院 | Synthesis and surface modification method of lithium excessive laminar oxide anode material |
| CN102738458A (en) * | 2012-06-13 | 2012-10-17 | 北京有色金属研究总院 | Surface modification method of lithium-rich cathode material |
| CN103441240A (en) * | 2013-08-02 | 2013-12-11 | 中国科学院长春应用化学研究所 | Single-step preparation method of surface coating and chemical activation lithium-rich solid solution anode material |
| CN104900860A (en) * | 2014-03-04 | 2015-09-09 | 北京有色金属研究总院 | Lithium-rich positive electrode material surface modification method, positive electrode containing surface-modified lithium-rich positive electrode material, and lithium ion battery |
| WO2016063281A1 (en) * | 2014-10-21 | 2016-04-28 | Ramot At Tel-Aviv University Ltd | High-capacity silicon nanowire based anode for lithium-ion batteries |
| CN104577101A (en) * | 2014-12-25 | 2015-04-29 | 芜湖市汽车产业技术研究院有限公司 | Preparation method for surface-modified lithium-manganese-rich cathode material of lithium ion battery |
| WO2017150915A1 (en) * | 2016-03-04 | 2017-09-08 | 주식회사 엘 앤 에프 | Positive electrode active material for lithium secondary battery, method for producing same and lithium secondary battery comprising same |
| CN106450194A (en) * | 2016-10-13 | 2017-02-22 | 华南师范大学 | Manganese-based lamellar lithium-rich material provided with uniform lithium phosphate coating layer and preparation method thereof |
| CN108075111A (en) * | 2016-11-18 | 2018-05-25 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and positive electrode material thereof |
| CN106602024A (en) * | 2016-12-28 | 2017-04-26 | 国联汽车动力电池研究院有限责任公司 | In-situ surface-modified lithium-rich material and preparation method thereof |
| CN106848227A (en) * | 2017-01-23 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified lithium-rich manganese-based anode material in surface |
| CN108172803A (en) * | 2017-12-30 | 2018-06-15 | 国联汽车动力电池研究院有限责任公司 | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery |
| CN108199024A (en) * | 2017-12-30 | 2018-06-22 | 国联汽车动力电池研究院有限责任公司 | A kind of rich lithium material of surface recombination cladding and preparation method thereof |
| CN108615875A (en) * | 2018-05-04 | 2018-10-02 | 中南大学 | A kind of lithium-rich manganese-based anode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| DENIS Y. W. YU等: ""Surface Modification of Li-Excess Mn-based Cathode Materials"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364703A (en) * | 2019-06-11 | 2019-10-22 | 浙江吉利控股集团有限公司 | A kind of composite material and preparation method thereof, anode, battery and preparation method thereof |
| CN110364703B (en) * | 2019-06-11 | 2021-02-26 | 浙江吉利控股集团有限公司 | Composite material preparation method, battery anode, battery and preparation method thereof |
| CN111422920A (en) * | 2019-12-26 | 2020-07-17 | 蜂巢能源科技有限公司 | Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery |
| CN114583120A (en) * | 2021-12-27 | 2022-06-03 | 武汉理工大学 | Method for designing and constructing gradient structure with metal ion component on surface of lithium-rich material |
| CN114583120B (en) * | 2021-12-27 | 2023-05-16 | 武汉理工大学 | Method for designing and constructing gradient structure with metal ion components on surface of lithium-rich material |
| CN115286042A (en) * | 2022-09-22 | 2022-11-04 | 河南电池研究院有限公司 | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof |
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