CN114023962B - LiAlSi4O10Coated lithium ion battery anode material and preparation method thereof - Google Patents
LiAlSi4O10Coated lithium ion battery anode material and preparation method thereof Download PDFInfo
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- CN114023962B CN114023962B CN202111214987.3A CN202111214987A CN114023962B CN 114023962 B CN114023962 B CN 114023962B CN 202111214987 A CN202111214987 A CN 202111214987A CN 114023962 B CN114023962 B CN 114023962B
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- Prior art keywords
- lithium
- precursor
- coated
- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 99
- 239000010405 anode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 238000000034 method Methods 0.000 claims abstract description 69
- 229910010100 LiAlSi Inorganic materials 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000011066 ex-situ storage Methods 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 338
- 150000002642 lithium compounds Chemical class 0.000 claims description 126
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 96
- 238000005245 sintering Methods 0.000 claims description 86
- 239000011572 manganese Substances 0.000 claims description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 81
- 229910052744 lithium Inorganic materials 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 238000001354 calcination Methods 0.000 claims description 69
- 239000007774 positive electrode material Substances 0.000 claims description 60
- 239000003570 air Substances 0.000 claims description 56
- 239000012298 atmosphere Substances 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 46
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 43
- 238000000576 coating method Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 43
- 238000005303 weighing Methods 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 38
- 239000001301 oxygen Substances 0.000 claims description 38
- 229910052760 oxygen Inorganic materials 0.000 claims description 38
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 27
- 238000006138 lithiation reaction Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013589 supplement Substances 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 17
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical group [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000010416 ion conductor Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 165
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 229940099596 manganese sulfate Drugs 0.000 description 14
- 239000011702 manganese sulphate Substances 0.000 description 14
- 235000007079 manganese sulphate Nutrition 0.000 description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 14
- 229940053662 nickel sulfate Drugs 0.000 description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000006174 pH buffer Substances 0.000 description 9
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 8
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 8
- 229940039790 sodium oxalate Drugs 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- 230000037427 ion transport Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940010048 aluminum sulfate Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007086 side 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a LiAlSi 4O10 -coated lithium ion battery anode material and a preparation method thereof. According to the invention, the lithium ion conductor LiAlSi 4O10 is coated on the lithium ion battery anode materials with different crystal structures by an in-situ and ex-situ chemical synthesis method. The lithium ion battery anode material prepared by the preparation method improves the lithium ion diffusion coefficient, the multiplying power performance, the interface stability and the cycle stability of the lithium ion battery anode material. The method has the advantages of obvious performance improvement, simple synthesis process, high production efficiency and good product uniformity, and is suitable for large-scale production. The method has the advantages of nontoxic raw materials, low cost, easily controlled reaction conditions, no need of special protection in the production process, high yield of the obtained product, good result repeatability and the like.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a LiAlSi 4O10 -coated lithium ion battery anode material and a preparation method thereof.
Background
The popularization of the lithium ion battery electric automobile is a state-driven energy reform, and is a key link for realizing carbon reaching peak and carbon neutralization. The core of an electric automobile is a battery, and the key of the battery is a positive electrode. At present, the anode material generally has the problems of slow interfacial lithium ion transmission and poor interfacial stability. For liquid batteries, interfacial lithium ion transport is slow limiting the charge-discharge rate of the positive electrode material at high current densities and the power density and fast charge implementation of lithium ion batteries. Meanwhile, under high voltage, the surface of the high-activity positive electrode material can undergo side reaction with electrolyte to generate gas, so that the impedance of the battery is increased. For solid state batteries, the rate of lithium ion transport and interfacial stability between the cathode materials and the solid state electrolyte largely determine the performance of the battery. The problems of slow interfacial lithium ion transmission and poor interfacial stability of the positive electrode material obviously limit the further development of liquid and solid batteries. Currently, the main strategies to improve the above problems are bulk doping and surface cladding. However, this problem is not solved well at present, since the improvement effect of general bulk doping and surface coating is not satisfactory. Therefore, it is very important and urgent to develop a method capable of improving interfacial lithium ion transport and interfacial stability of a positive electrode material with high efficiency.
Disclosure of Invention
The invention aims at least solving the technical problems, and provides a LiAlSi 4O10 coated lithium ion battery anode material and a preparation method thereof, wherein the lithium ion battery anode material with different crystal structures is coated with a fast lithium ion conductor LiAlSi 4O10 by an in-situ and ex-situ chemical synthesis method. Therefore, the interfacial lithium ion diffusion coefficient, the multiplying power performance, the interfacial stability and the cycling stability of the positive electrode material of the lithium ion battery are improved.
In a first aspect of the present invention, a lithium ion battery positive electrode material coated with liaalsi 4O10 is provided, and an intermediate product Al (Si 2O5)2, i.e., a solid phase synthesis method is used to coat the lithium ion battery positive electrode material with liaalsi 4O10, where the lithium ion battery positive electrode material is a layered oxide, a lithium-rich manganese-based oxide, olivine-type lithium iron phosphate, or spinel-type lithium manganate.
In a second aspect of the present invention, a preparation method for coating a positive electrode material of a lithium ion battery with liaalsi 4O10 using an in-situ coating method is provided, including the following steps:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to ensure that the total molar concentration of M ions is more than or equal to 1mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the solution M and the precipitant solution, stirring at the same time, controlling the reaction temperature to be 30-85 ℃ for 10-48 hours, regulating the pH value of the solution to be 8-12 by using a pH regulator in the reaction process, introducing a protective gas which is nitrogen, argon or carbon dioxide when regulating the pH value, centrifuging or suction-filtering the precipitate obtained by the reaction, and drying to obtain a precursor;
(2) Coating oxide by hydrolysis method or mixing method:
Adopts a hydrolysis method:
Weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of M in the ethyl orthosilicate to Si in the aluminum isopropoxide of 100 to alpha to beta, wherein 0.4< alpha <10,0.1< beta <2.5; dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100 epsilon to delta, 2 epsilon <2000,0.02< delta <0.5, and carrying out suction filtration and drying to obtain powder; calcining the powder in an air atmosphere, an oxygen atmosphere or a nitrogen atmosphere at 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor), wherein the precipitant in the step (1) is in the nitrogen atmosphere when the precipitant is phosphate, and the rest is oxygen, air or nitrogen;
or a mixing method is adopted:
Weighing the silicon oxide, silicate or silicon-containing organic matter and aluminum oxide or salt according to the mole ratio of Si to Al in the silicon oxide, silicate or silicon-containing organic matter to Al in the aluminum oxide or salt of 4:1; uniformly mixing weighed matters, calcining in oxygen or air atmosphere to prepare Al (Si 2O5)2, wherein the calcining temperature is 300-1100 ℃ and the calcining time is 0.5-18 hours, and weighing the precursor and Al (Si 2O5)2) according to the M in the precursor, wherein the molar ratio of Al in the precursor to Al (Si 2O5)2 is 100:beta, 0.1< beta <2.5, and the mixture of Al (Si 2O5)2 and the precursor is obtained;
(3) Lithiation treatment was performed on a mixture of Al (Si 2O5)2 and precursor:
(3-1) mixing Al (mixture of Si 2O5)2 and precursor) with a lithium compound by any one of the following methods:
The first method is as follows:
For layered oxides and lithium iron phosphate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: li in lithium compound is (100+beta) [ (100+beta) ×1.05], and uniformly mixing the weighed substances to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100 corresponds to M in the precursor, is the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, beta corresponds to Al (Al in Si 2O5)2, is the theoretical lithium amount of the Al (Si 2O5)2 converted into LiAlSi 4O10, and is more than 5% of lithium to supplement the volatilized lithium amount when 1.05 is sintered at high temperature), and 0.1< beta <2.5;
The second method is as follows:
For lithium-rich manganese-based oxides: according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound is (100+beta) { [ (100+pi) +beta ]. Times.1.05 }, weighing the Al (Si 2O5)2 coated precursor and the lithium compound, and uniformly mixing the weighed matters to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, and beta corresponds to the theoretical lithium amount of Al (Al in Si 2O5)2, al (Si 2O5)2 converted into LiAlSi 4O10, and 1.05 is the theoretical lithium amount required to be added by 5% during high-temperature sintering to supplement volatilized lithium, pi is more than or equal to 100, and 0.1< beta is less than 2.5;
The third method is as follows:
For lithium manganate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor being (100+beta): [ (50+beta). Times.1.05 ], and uniformly mixing to obtain Al (Si 2O5)2/precursor mixture of the lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate), 100 corresponds to M in the precursor, beta corresponds to Al (Al in Si 2O5)2, theoretical lithium amount of the Al converted into LiAlSi 4O10 is Al (Si 2O5)2), and 1.05 is the lithium amount required to be added by 5% during high-temperature sintering to supplement the volatilized lithium amount, and 0.1< beta <2.5;
and (3-2) calcining the Al (Si 2O5)2/precursor mixture of the lithium compound in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain the LiAlSi 4O10 coated lithium ion battery anode material.
In a third aspect of the present invention, a method for preparing a lithium ion battery positive electrode material coated with liaalsi 4O10 by an ex-situ coating method is also provided, including:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to make the total molar concentration of M ions be more than or equal to 1mol/L, and dissolving precipitant in water to make the molar concentration of precipitant be more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the solution M and the precipitant solution, stirring, controlling the temperature to be 30-85 ℃ during the reaction, controlling the reaction time to be 10-48 hours, regulating the pH value of the solution to be 8-12 by using a pH regulator during the reaction, introducing a protective gas which is nitrogen, argon or carbon dioxide during the regulation of the pH value, centrifuging or filtering and separating the precipitate obtained by the reaction, and drying to obtain a precursor;
(2) Preparing a positive electrode material:
(2-1) mixing the precursor with a lithium compound by any one of the following methods:
The first method is as follows:
For conventional layered oxides and lithium iron phosphate: according to the molar ratio of Li in the lithium compound in the precursor being 100 [ (100) multiplied by 1.05], weighing the precursor and the lithium compound, and uniformly mixing the weighed matters to obtain the precursor of the well mixed lithium compound, wherein 100 corresponds to M in the precursor, namely the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount during high-temperature sintering;
The second method is as follows:
For lithium-rich manganese-based oxides: the molar ratio of Li in the lithium compound in the precursor obtained in the step 1 is 100 [ (100+pi) ×1.05], the precursor and the lithium compound are weighed and uniformly mixed to obtain the precursor of the well mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, 100 corresponds to M in the precursor, and more than 5% of lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering, and pi is more than or equal to 0 and less than or equal to 100;
The third method is as follows:
And (2) for lithium manganate, according to the molar ratio of M in the lithium compound in the precursor obtained in the step (1) being 100, (50 multiplied by 1.05), weighing the precursor and the lithium compound, and uniformly mixing the precursor and the lithium compound to obtain the precursor of the well mixed lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate, 100 corresponds to M in the precursor, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount when sintering at high temperature;
(2-2) placing the precursor of the mixed lithium compound in air, oxygen or nitrogen atmosphere for calcination, wherein the sintering temperature is 600-1200 ℃, the sintering time is 5-22 hours, and cooling to room temperature to obtain the lithium ion battery anode material;
(3) Preparation of Al (Si 2O5)2:
Weighing raw materials according to the mole ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matters of 1:4, uniformly mixing the weighed materials, calcining in oxygen or air atmosphere at the calcining temperature of 300-1100 ℃ for 0.5-18 hours to obtain Al (Si 2O5)2;
(4) Coating LiAlSi 4O10 on a lithium ion battery anode material:
Weighing raw materials according to the molar ratio of M to Al (Al in Si 2O5)2 to Li in lithium compound) in the positive electrode material (or purchased positive electrode material) of 100 to beta, uniformly mixing the weighed materials, wherein 0.1 to beta is less than 2.5, calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5 to 6 hours, calcining at 300 to 700 ℃, and naturally cooling to room temperature to obtain the lithium ion battery positive electrode material coated by LiAlSi 4O10.
The LiAlSi 4O10 coated lithium ion battery anode material prepared by the method has the advantages of obvious performance improvement, simple synthesis process, high production efficiency and good product uniformity, and is suitable for large-scale production. The preparation method has the advantages of non-toxic raw materials, low cost, easily controlled reaction conditions, no need of special protection in the production process, high yield of the obtained product, good result repeatability and the like.
In some embodiments, the method for preparing a positive electrode material of a lithium ion battery is characterized in that when M is a metal, the metal is one or more of Ni, co, mn, al, fe, ti, zr, mg, V, nb, ga, sn, sc, cu, la, ca, Y, mo, zn, cr, ce.
In some embodiments, the soluble salt of M is a sulfate, nitrate, acetate, sulfite, or nitrite.
In some embodiments, the precipitating agent is one or more of oxalate, carbonate, hydroxide, and phosphate.
In some embodiments, the alcohol is one or more of ethanol, propanol, isopropanol, butanol; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, tartaric acid and oxalic acid.
In some embodiments, the lithium compound is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate.
According to the preparation method provided by the embodiment of the invention, the lithium ion conductor LiAlSi 4O10 is coated on the lithium ion battery anode materials with different crystal structures by an in-situ and ex-situ chemical synthesis method. Therefore, the interfacial lithium ion diffusion coefficient, the multiplying power performance, the interfacial stability and the cycling stability of the positive electrode material of the lithium ion battery are improved. The method has the advantages of simple synthesis process, high production efficiency and good product uniformity, and is suitable for large-scale production. The method has the advantages of readily available reaction raw materials, no toxicity, low cost, no special protection in the production process, easy control of reaction conditions, high yield of the obtained product, good result repeatability and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings by those of ordinary skill in the art without inventive effort.
Fig. 1 shows XRD patterns of a positive electrode material of a lithium ion battery, wherein (a) is an XRD pattern of a positive electrode material of a lithium ion battery coated with liaalsi 4O10 prepared in example 1 of the present invention, and (b) is an XRD pattern of a positive electrode material of an unmodified lithium ion battery.
In fig. 2, (a) is a schematic diagram of specific discharge capacity cycle of the liaalsi 4O10 coated lithium ion battery cathode material prepared in example 1 of the present invention under the condition of 1C (250 mA/g) and 4.8V cut-off voltage, and (b) is a schematic diagram of specific discharge capacity cycle of the unmodified lithium ion battery cathode material under the condition of 1C (250 mA/g) and 4.8V cut-off voltage.
Fig. 3 is a graph showing the ratio of liaalsi 4O10 coated lithium ion battery positive electrode material prepared in example 1 of the present invention to unmodified lithium ion battery positive electrode material.
Fig. 4 is a comparison of impedance spectra of liaalsi 4O10 coated lithium ion battery positive electrode materials prepared in accordance with an embodiment of the present invention and unmodified lithium ion battery positive electrode materials.
Detailed Description
The following detailed description of embodiments of the invention, examples of which are illustrated in the accompanying drawings and, by way of example, are intended to be illustrative, and not to be construed as limiting, of the invention.
The embodiment of the invention provides a LiAlSi 4O10 coated lithium ion battery anode material, which is prepared by coating lithium ion battery anode materials with different crystal structures by using an intermediate product Al (Si 2O5)2) and adopting a solid-phase synthesis method, wherein the lithium ion battery anode material is layered oxide, lithium-rich manganese-based oxide, olivine-type lithium iron phosphate or spinel-type lithium manganate.
Compared with the unmodified lithium ion battery anode material, the LiAlSi 4O10 coated lithium ion battery anode material prepared by the embodiment of the invention has the advantages of remarkably improving the interface lithium ion diffusion coefficient, the multiplying power performance, the interface stability and the cycle stability.
The embodiment of the invention also provides a preparation method of the LiAlSi 4O10 coated lithium ion battery anode material, which adopts an in-situ coating method and comprises the following steps:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to ensure that the total molar concentration of M ions is more than or equal to 1mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the M solution and the precipitant solution, and dropwise adding the mixture into a reaction kettle together, or dropwise adding the precipitant solution into a reaction kettle containing the M solution, or dropwise adding the M solution into the reaction kettle containing the precipitant solution, and stirring at the same time. In the reaction process, the pH value of the solution can be regulated and controlled to be 8-12 by utilizing a pH regulator, protective gas is introduced when regulating and controlling the pH value, the protective gas is nitrogen, argon or carbon dioxide, the temperature is controlled to be 30-85 ℃ during the reaction, the time is controlled to be 10-48 hours, and a precipitate obtained by the reaction is centrifuged or filtered and separated by suction, and a precursor is obtained after drying;
(2) Coating oxide by hydrolysis method or mixing method:
Adopts a hydrolysis method:
Weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of M in the precursor (or M in the purchased precursor) to Si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100 to alpha to beta, wherein 0.4< alpha <10,0.1< beta <2.5; dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100 epsilon to delta, 2 epsilon <2000,0.02< delta <0.5, and carrying out suction filtration and drying to obtain powder; calcining the powder in an air atmosphere, an oxygen atmosphere or a nitrogen atmosphere at 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor), wherein the precipitant in the step (1) is in the nitrogen atmosphere when the precipitant is phosphate, and the rest is oxygen, air or nitrogen;
or a mixing method is adopted:
Weighing the silicon oxide, silicate or silicon-containing organic matter and aluminum oxide or salt according to the mole ratio of Si to Al in the silicon oxide, silicate or silicon-containing organic matter to Al in the aluminum oxide or salt of 4:1; uniformly mixing the weighed substances, calcining in oxygen or air atmosphere to prepare Al (Si 2O5)2, wherein the calcining temperature is 300-1100 ℃ and the calcining time is 0.5-18 hours, and according to M in the precursor (or M in the purchased precursor), the molar ratio of Al in the prepared Al (Si 2O5)2) is 100:beta, 0.1< beta <2.5, the precursor and Al (Si 2O5)2) are weighed, and the weighed substances are uniformly mixed to obtain Al (Si 2O5)2 and the mixture of the precursor;
(3) Lithiation treatment was performed on a mixture of Al (Si 2O5)2 and precursor:
(3-1) mixing Al (mixture of Si 2O5)2 and precursor) with a lithium compound by any one of the following methods:
The first method is as follows:
For conventional layered oxides and lithium iron phosphate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: li in lithium compound is (100+beta) [ (100+beta) ×1.05], and uniformly mixing the weighed substances to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100 corresponds to M in the precursor, is the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, beta corresponds to Al (Al in Si 2O5)2, is the theoretical lithium amount of the Al (Si 2O5)2 converted into LiAlSi 4O10, and is more than 5% of lithium to supplement the volatilized lithium amount when 1.05 is sintered at high temperature), and 0.1< beta <2.5;
The second method is as follows:
For lithium-rich manganese-based oxides: according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound is (100+beta) { [ (100+pi) +beta ]. Times.1.05 }, weighing the Al (Si 2O5)2 coated precursor and the lithium compound, and uniformly mixing the weighed matters to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, and beta corresponds to the theoretical lithium amount of Al (Al in Si 2O5)2, al (Si 2O5)2 converted into LiAlSi 4O10, and 1.05 is the theoretical lithium amount required to be added by 5% during high-temperature sintering to supplement volatilized lithium, pi is more than or equal to 100, and 0.1< beta is less than 2.5;
The third method is as follows:
For lithium manganate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor being (100+beta): [ (50+beta). Times.1.05 ], and uniformly mixing to obtain Al (Si 2O5)2/precursor mixture of the lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate), 100 corresponds to M in the precursor, beta corresponds to Al (Al in Si 2O5)2, theoretical lithium amount of the Al converted into LiAlSi 4O10 is Al (Si 2O5)2), and 1.05 is the lithium amount required to be added by 5% during high-temperature sintering to supplement the volatilized lithium amount, and 0.1< beta <2.5;
and (3-2) calcining the Al (Si 2O5)2/precursor mixture of the lithium compound in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain the LiAlSi 4O10 coated lithium ion battery anode material.
The embodiment of the invention also provides another preparation method of the LiAlSi 4O10 coated lithium ion battery anode material, which adopts an ex-situ coating method and comprises the following steps:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to make the total molar concentration of M ions be more than or equal to 1mol/L, and dissolving precipitant in water to make the molar concentration of precipitant be more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the solution M and the solution of the precipitant, adding the mixture into a reaction kettle dropwise together, or adding the solution of the precipitant into the reaction kettle containing the solution M dropwise, or adding the solution M into the reaction kettle containing the solution of the precipitant dropwise while stirring, regulating the pH value of the solution to 8-12 by using a pH regulator in the reaction process, introducing a protective gas which is nitrogen, argon or carbon dioxide when regulating the pH value, controlling the temperature to 30-85 ℃ for 10-48 hours during the reaction, centrifuging or suction-filtering the precipitate obtained by the reaction, and drying to obtain a precursor;
(2) Preparing a positive electrode material:
(2-1) mixing the precursor with a lithium compound by any one of the following methods:
The first method is as follows:
For conventional layered oxides and lithium iron phosphate: according to the molar ratio of Li in the lithium compound in the precursor being 100 [ (100) multiplied by 1.05], weighing the precursor and the lithium compound, and uniformly mixing the weighed matters to obtain the precursor of the well mixed lithium compound, wherein 100 corresponds to M in the precursor, and is the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount during high-temperature sintering;
The second method is as follows:
For lithium-rich manganese-based oxides: the molar ratio of Li in the lithium compound in the precursor obtained in the step 1 is 100 [ (100+pi) ×1.05], the precursor and the lithium compound are weighed and uniformly mixed to obtain the precursor of the well mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, 100 corresponds to the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, and 1.05 is obtained by adding more than 5% of lithium to supplement the volatilized lithium amount during high-temperature sintering, and pi is more than or equal to 0 and less than or equal to 100;
The third method is as follows:
And (2) for lithium manganate, according to the molar ratio of M in the lithium compound in the precursor obtained in the step (1) being 100, (50 multiplied by 1.05), weighing the precursor and the lithium compound, and uniformly mixing the precursor and the lithium compound to obtain the precursor of the well mixed lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate, 100 corresponds to the theoretical lithium amount of M in the precursor, which is the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, and 1.05 is obtained by adding more than 5% of lithium to supplement the volatilized lithium amount during high-temperature sintering;
(2-2) placing the precursor of the mixed lithium compound in air, oxygen or nitrogen atmosphere for calcination, wherein the sintering temperature is 600-1200 ℃, the sintering time is 5-22 hours, and cooling to room temperature to obtain the lithium ion battery anode material;
(3) Preparation of Al (Si 2O5)2:
Weighing raw materials according to the mole ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matters of 1:4, uniformly mixing the weighed materials, calcining in oxygen or air atmosphere at the calcining temperature of 300-1100 ℃ for 0.5-18 hours to obtain Al (Si 2O5)2;
(4) Coating LiAlSi 4O10 on a lithium ion battery anode material:
Weighing raw materials according to the molar ratio of M to Al (Al in Si 2O5)2 to Li in lithium compound) in the positive electrode material (or purchased positive electrode material) of 100 to beta, uniformly mixing the weighed materials, wherein 0.1 to beta is less than 2.5, calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5 to 6 hours, calcining at 300 to 700 ℃, and naturally cooling to room temperature to obtain the lithium ion battery positive electrode material coated by LiAlSi 4O10.
In some embodiments, when the M is a metal, the metal is one or more of Ni, co, mn, al, fe, ti, zr, mg, V, nb, ga, si, sn, sc, cu, la, ca, Y, mo, zn, cr, ce, B.
In some embodiments, the soluble salt of M is a sulfate, nitrate, acetate, sulfite, or nitrite.
In some embodiments, the precipitating agent is one or more of oxalate, carbonate, hydroxide, and phosphate.
In some embodiments, the alcohol is one or more of ethanol, propanol, isopropanol, butanol; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, tartaric acid and oxalic acid.
In some embodiments, the lithium compound is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate.
According to the embodiment of the invention, the preparation method of the LiAlSi 4O10 coated lithium ion battery anode material improves the lithium ion diffusion coefficient, the rate capability, the interface stability and the cycle stability of the lithium ion battery anode material. The method has the advantages of obvious performance improvement, simple synthesis process, high production efficiency and good product uniformity, and is suitable for large-scale production. The method has the advantages of nontoxic raw materials, low cost, easily controlled reaction conditions, no need of special protection in the production process, high yield of the obtained product, good result repeatability and the like.
The method for preparing the LiAlSi 4O10 coated lithium ion battery cathode material is described in further detail below with reference to examples.
Example 1:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel sulfate and manganese sulfate were dissolved in water at a molar ratio of Ni to Mn of 1:3, and at the same time, at a total metal ion molar concentration of 2mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: according to the molar ratio of oxalic acid in the solution of the precipitant to the solution of the (Ni+Mn) in the solution of the M being 1:1, the solution of the M and the solution of the precipitant are added into a reaction kettle drop by drop together. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the tetraethoxysilane and the aluminum isopropoxide according to the molar ratio of (Ni+Mn) in the precursor prepared in the step 1, si in the tetraethoxysilane and Al in the aluminum isopropoxide of 100:0.8:0.2. Dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of ethanol and deionized water in a molar ratio of ammonia water of 100:10:0.1. Heating and stirring in the reaction process, and reacting for 2.5 hours at the temperature of 40 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 500 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound is (100+0.2): { [ (100+25) +0.2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 900 ℃, and the sintering time is 12 hours.
Fig. 1 shows XRD patterns of a positive electrode material of a lithium ion battery, wherein (a) is an XRD pattern of a positive electrode material of a lithium ion battery coated with liaalsi 4O10 prepared in example 1 of the present invention, and (b) is an XRD pattern of a positive electrode material of an unmodified lithium ion battery.
In fig. 2, (a) is a schematic diagram of specific discharge capacity cycle of the liaalsi 4O10 coated lithium ion battery cathode material prepared in example 1 of the present invention under the condition of 1C (250 mA/g) and 4.8V cut-off voltage, and (b) is a schematic diagram of specific discharge capacity cycle of the unmodified lithium ion battery cathode material under the condition of 1C (250 mA/g) and 4.8V cut-off voltage.
Fig. 3 is a graph showing the ratio of liaalsi 4O10 coated lithium ion battery positive electrode material prepared in example 1 of the present invention to unmodified lithium ion battery positive electrode material.
Fig. 4 is a comparison of impedance spectra of liaalsi 4O10 coated lithium ion battery positive electrode materials prepared in accordance with an embodiment of the present invention and unmodified lithium ion battery positive electrode materials.
Example 2:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 1:1:4, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium oxalate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Co+Mn) to sodium oxalate of 1:1 in the M solution. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Co+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:2:0.5. The weighed precursor, tetraethoxysilane and aluminum isopropoxide are dispersed/dissolved in a mixed solvent of isopropanol and deionized water in a molar ratio of hydrochloric acid of 100:15:0.02. Heating and stirring in the reaction process, and reacting for 1 hour at the temperature of 70 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 600 ℃ for 10 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (Ni+Co+Mn) +Al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+0.5) { [ (100+25) +0.5 ]. Times.1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 950 ℃ and the sintering time is 18 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 3:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 8:1:1, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium oxalate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Co+Mn) to sodium oxalate of 1:1.02 in the M solution. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Co+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:2:0.5. The weighed precursor, tetraethoxysilane and aluminum isopropoxide are dispersed/dissolved in a mixed solvent of isopropanol and deionized water in a molar ratio of hydrochloric acid of 100:15:0.02. Heating and stirring in the reaction process, and reacting for 0.5 hour at the temperature of 90 ℃. After the reaction is completed, the solution is filtered and dried. And calcining the obtained powder in nitrogen at 300 ℃ for 15 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (ni+co+mn) +al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+0.5): { [ (100+0) +0.5] ×1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 700 ℃ and the sintering time is 10 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 4:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel nitrate, cobalt nitrate and manganese nitrate are dissolved in water, the molar ratio of Ni to Co to Mn is 7:1.5:1.5, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: and adding the M solution and the precipitant solution into a reaction kettle drop by drop according to the molar ratio of the (Ni+Co+Mn) in the M solution to the sodium hydroxide in the precipitant solution being 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.5, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Co+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:4:1. The weighed precursor, tetraethoxysilane and aluminum isopropoxide are dispersed/dissolved in a mixed solvent of propanol and deionized water in a molar ratio of 100:100:0.02. Heating and stirring in the reaction process, and reacting for 16 hours at the temperature of 40 ℃. After the reaction is completed, the solution is filtered and dried. And calcining the obtained powder in air at 670 ℃ for 7 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (Ni+Co+Mn) +Al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+1): { [ (100+0) +1 ]. Times.1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 750 ℃, and the sintering time is 12 hours.
Example 5:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution, namely dissolving nickel sulfate and manganese sulfate into water, enabling the molar ratio of Ni to Mn to be 1.1:3, and enabling the total molar concentration of metal ions to be 2mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Mn) oxalic acid in the precipitant solution of 1:1.03. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:2:0.5. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of ethanol and deionized water in a molar ratio of hydrochloric acid of 100:200:0.02. The reaction is carried out for 10 minutes at 55 ℃ under heating and stirring. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in oxygen at 300 ℃ for 0.5h to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2) -coated precursor obtained: the molar ratio of Li in the lithium compound was (100+0.5) { [ (100+22) +0.5 ]. Times.1.05 }, al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 870 ℃, and the sintering time is 24 hours.
Example 6:
Step 1, preparing a precursor:
preparing M solution and precipitant solution, namely dissolving cobalt acetate in water to make the molar concentration of Co ions be 1mol/L. The precipitant sodium carbonate was dissolved in water to a molar concentration of 1mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of Co to sodium carbonate in the precipitant solution of 1:1.03. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
and (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of Co in the precursor prepared in the step (1) to Si in the ethyl orthosilicate to Al in the aluminum isopropoxide of 100:4:1. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of ethanol and deionized water in a molar ratio of hydrochloric acid of 100:220:0.1. Heating and stirring in the reaction process, and reacting for 0.5 hour at the temperature of 45 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in oxygen at 300 ℃ for 0.5h to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
According to the 2 nd step [ the total amount of Co+ coated Al (Al in Si 2O5)2) in the obtained Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound was (100+1): { [ (100+0) +1 ]. Times.1.05 }, al (Si 2O5)2 coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 920 ℃, the sintering time is 16 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 7:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: manganese sulfate was dissolved in water so that the molar concentration of Mn ions was 1mol/L. The precipitant sodium carbonate was dissolved in water to a molar concentration of 1mol/L.
Precipitation reaction: the precipitant solution was added dropwise to the M solution at a molar ratio of Mn to sodium carbonate in the precipitant solution of 1:1.01. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the mole ratio of Mn in the precursor prepared in the step (1) to Si in the ethyl orthosilicate to Al in the aluminum isopropoxide of 100:4:1. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of ethanol and deionized water in a molar ratio of hydrochloric acid of 100:250:0.1. Heating and stirring in the reaction process, and reacting for 10 hours at the temperature of 35 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in oxygen at 500 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
according to the 2 nd step [ the total amount of Mn+coated Al (Al in Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound is (100+1): { [ (100+100) +1 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide) were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 800 ℃, and the sintering time is 18 hours.
Example 8:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: manganese sulfate was dissolved in water so that the molar concentration of Mn ions was 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added into the reaction kettle dropwise according to the total molar ratio of Mn to sodium hydroxide in the M solution of 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.3, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the mole ratio of Mn in the precursor prepared in the step (1) to Si in the ethyl orthosilicate to Al in the aluminum isopropoxide of 100:8:2. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:300:1. Heating and stirring in the reaction process, and reacting for 1 hour at the temperature of 85 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 1000 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 coated precursor).
Step 3, lithiation:
according to the 2 nd step [ the total amount of Mn+coated Al (Al in Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound was (100+2): { [ (50) +2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 850 ℃, and the sintering time is 20 hours.
Example 9:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate and manganese sulfate were dissolved in water at a molar ratio of Ni to Mn of 1:3, and at the same time, at a total metal ion molar concentration of 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added into a reaction kettle dropwise according to the molar ratio of the (Ni+Mn) in the M solution to the sodium hydroxide in the precipitant solution being 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.3, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:8:2. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:300:1. Heating and stirring in the reaction process, and reacting for 1 hour at the temperature of 85 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 1000 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 coated precursor).
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2 -coated precursor obtained: the molar ratio of Li in the lithium compound is (100+2) { [ (50) +2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 880 ℃, the sintering time is 22 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 10:
Step 1, preparing a precursor:
preparing M solution and precipitant solution, namely dissolving ferrous sulfate in water to make the molar concentration of Fe ions be 2mol/L. The precipitant sodium phosphate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: and adding the M solution and the precipitant solution into a reaction kettle dropwise according to the molar ratio of Fe in the M solution to sodium phosphate in the precipitant solution being 3:2. And nitrogen is introduced in the reaction process for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of Fe in the precursor prepared in the step (1) to Si in the ethyl orthosilicate to Al in the aluminum isopropoxide of 100:2:0.5. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of butanol, deionized water and tartaric acid in a molar ratio of 100:500:1. Heating and stirring in the reaction process, and reacting for 2 hours at the temperature of 65 ℃. After the reaction is completed, the solution is filtered and dried. And calcining the obtained powder in nitrogen at 400 ℃ for 12 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor).
Step 3, lithiation:
According to the 2 nd step [ the total amount of Fe+ coated Al (Al in Si 2O5)2) in the obtained Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound was (100+0.5) { [100+0.5 ]. Times.1.05 }, al (Si 2O5)2 coated precursor and lithium hydroxide) were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in nitrogen atmosphere for calcination, wherein the sintering temperature is 1000 ℃ and the sintering time is 16 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 11:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 1:1:1, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added dropwise into a reaction kettle according to the molar ratio of the sodium hydroxide in the precipitant solution of (Ni+Co+Mn) in the M solution of 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.0, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Co+Mn) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:10:2.5. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of butanol and deionized water in a molar ratio of 100:2000:0.02. Heating and stirring in the reaction process, and reacting for 4 hours at the temperature of 35 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 400 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 coated precursor).
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the molar ratio of Li in the lithium compound of (100+2): { [ (100) +2 ]. Times.1.05 } in the Al (Si 2O5)2) -coated precursor obtained (Ni+Co+Mn) +coated Al (Si 2O5)2).
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 880 ℃, the sintering time is 17 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 12:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and aluminum sulfate are dissolved in water, the molar ratio of Ni to Co to Al is 0.8:0.15:0.05, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added into a reaction kettle dropwise according to the molar ratio of the sodium hydroxide in the precipitant solution of (Ni+Co+Al) in the M solution of 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.8, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
And (2) weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of (Ni+Co+Al) in the precursor prepared in the step 1, si in the ethyl orthosilicate and Al in the aluminum isopropoxide of 100:10:2.5. And dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent of butanol and deionized water in a molar ratio of 100:2000:0.02. Heating and stirring in the reaction process, and reacting for 4 hours at the temperature of 35 ℃. After the reaction is completed, the solution is filtered and dried. Calcining the obtained powder in air at 400 ℃ for 5 hours to obtain an intermediate product Al (Si 2O5)2 coated precursor).
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the molar ratio of Li in the lithium compound of (100+2): { [ (100) +2 ]. Times.1.05 } in the Al (Si 2O5)2) -coated precursor obtained (Ni+Co+Al) +coated Al (Si 2O5)2).
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 750 ℃, and the sintering time is 17 hours.
Example 13:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution, namely dissolving nickel sulfate and manganese sulfate into water, enabling the molar ratio of Ni to Mn to be 1:3, and enabling the total molar concentration of metal ions to be 2mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: according to the molar ratio of oxalic acid in the solution of the precipitant to the solution of the (Ni+Mn) in the solution of the M being 1:1, the solution of the M and the solution of the precipitant are added into a reaction kettle drop by drop together. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 800℃for 5 hours in an air atmosphere to prepare Al (Si 2O5)2. Then (Ni+Mn) in the precursor prepared in step 1: al (molar ratio of Al in Si 2O5)2: 100:0.2), the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound is (100+0.2): { [ (100+25) +0.2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 900 ℃, and the sintering time is 12 hours.
Example 14:
step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 1:1:4, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium oxalate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Co+Mn) to sodium oxalate of 1:1 in the M solution. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
the silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 900 c in an air atmosphere for 5 hours to prepare Al (Si 2O5)2. Subsequently, in the precursor prepared in step 1, (ni+co+mn): the molar ratio of Al in the prepared Al (Si 2O5)2) was 100:0.5, the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (Ni+Co+Mn) +Al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+0.5) { [ (100+25) +0.5 ]. Times.1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 950 ℃ and the sintering time is 18 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 15:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 8:1:1, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium oxalate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Co+Mn) to sodium oxalate of 1:1.02 in the M solution. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silicon dioxide and the aluminum ethoxide are weighed according to the mole ratio of Si in the silicon dioxide to Al in the aluminum ethoxide of 4:1. The mixture was uniformly mixed and calcined at 850℃for 10 hours in an air atmosphere to prepare Al (Si 2O5)2. Then, in the precursor prepared in step 1, (Ni+Co+Mn): the molar ratio of Al in Si 2O5)2 was 100:0.5, the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (ni+co+mn) +al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+0.5): { [ (100+0) +0.5] ×1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 700 ℃ and the sintering time is 10 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 16:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel nitrate, cobalt nitrate and manganese nitrate are dissolved in water, the molar ratio of Ni to Co to Mn is 7:1.5:1.5, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: and adding the M solution and the precipitant solution into a reaction kettle drop by drop according to the molar ratio of the (Ni+Co+Mn) in the M solution to the sodium hydroxide in the precipitant solution being 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.5, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
Weighing the tetraethyl silicate and the aluminum ethoxide according to the molar ratio of Si in the tetraethyl silicate to Al in the aluminum ethoxide of 4:1. The mixture was uniformly mixed and calcined at 1000℃for 12 hours in an air atmosphere to prepare Al (Si 2O5)2. Then, in the precursor prepared in step 1, (Ni+Co+Mn): the molar ratio of Al in Si 2O5)2 was 100:1, the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the 2 nd step [ the total amount of (Ni+Co+Mn) +Al (Si 2O5)2) -coated Al in the resulting Al (Si 2O5)2) -coated precursor: the molar ratio of Li in the lithium compound was (100+1): { [ (100+0) +1 ]. Times.1.05 }.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 750 ℃, and the sintering time is 12 hours.
Example 17:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate and manganese sulfate were dissolved in water at a molar ratio of Ni to Mn of 1.1:3, and at the same time, at a total metal ion molar concentration of 2mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of (Ni+Mn) oxalic acid in the precipitant solution of 1:1.03. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The tetraethyl silicate and the aluminum nitrate are weighed according to the mole ratio of Si in the tetraethyl silicate to Al in the aluminum nitrate of 4:1. The mixture was uniformly mixed and then calcined at 1050℃for 16 hours in an air atmosphere to prepare Al (Si 2O5)2. In the precursor prepared in step 1, (Ni+Mn): the molar ratio of Al in the prepared Al (Si 2O5)2) was 100:0.5, the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2) -coated precursor obtained: the molar ratio of Li in the lithium compound was (100+0.5) { [ (100+22) +0.5 ]. Times.1.05 }, al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 870 ℃, and the sintering time is 24 hours.
Example 18:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: cobalt acetate was dissolved in water to give a molar concentration of Co ions of 1mol/L. The precipitant sodium carbonate was dissolved in water to a molar concentration of 1mol/L.
Precipitation reaction: the M solution was added dropwise to the precipitant solution in a molar ratio of Co to sodium carbonate in the precipitant solution of 1:1.03. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silicon dioxide and the aluminum nitrate are weighed according to the mole ratio of Si in the silicon dioxide to Al in the aluminum nitrate of 4:1. The mixture was uniformly mixed and then calcined at 800℃for 18 hours in an air atmosphere to prepare Al (Si 2O5)2. Then (Ni+Mn) in the precursor prepared in step 1: al (molar ratio of Al in Si 2O5)2: 100:1), the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
According to the 2 nd step [ the total amount of Co+ coated Al (Al in Si 2O5)2) in the obtained Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound was (100+1): { [ (100+0) +1 ]. Times.1.05 }, al (Si 2O5)2 coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 920 ℃, the sintering time is 16 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 19:
Step 1, oxide coating:
The silicon dioxide and the aluminum nitrate are weighed according to the mole ratio of Si in the silicon dioxide to Al in the aluminum nitrate of 4:1. The mixture was uniformly mixed and calcined at 800℃for 18 hours in an air atmosphere to prepare Al (Si 2O5)2. Subsequently, according to the Mn in the purchased manganese hydroxide precursor, the prepared Al (molar ratio of Al in Si 2O5)2: 100:1), the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 2, lithiation:
according to the 2 nd step [ the total amount of Mn+coated Al (Al in Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound is (100+1): { [ (100+100) +1 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide) were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 800 ℃, and the sintering time is 18 hours.
Example 20:
Step 1, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and calcined at 800℃for 18 hours in an air atmosphere to prepare Al (Si 2O5)2. Subsequently, according to the Mn in the purchased manganese hydroxide precursor, the prepared Al (molar ratio of Al in Si 2O5)2: 100:1), the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 2, lithiation:
according to the 2 nd step [ the total amount of Mn+coated Al (Al in Si 2O5)2) in the Al (Si 2O5)2 -coated precursor; the molar ratio of Li in the lithium compound was (100+2): { [ (50) +2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 850 ℃, and the sintering time is 20 hours.
Example 21:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate and manganese sulfate were dissolved in water at a molar ratio of Ni to Mn of 1:3, and at the same time, at a total metal ion molar concentration of 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added into a reaction kettle dropwise according to the molar ratio of the (Ni+Mn) in the M solution to the sodium hydroxide in the precipitant solution being 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.3, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 600℃for 17 hours in an air atmosphere to prepare Al (Si 2O5)2. Then (Ni+Mn) in the precursor prepared in step 1: al (molar ratio of Al in Si 2O5)2: 100:2), the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
According to the 2 nd step [ the total amount of (Ni+Mn) +Al (Si 2O5)2) in the Al (Si 2O5)2 -coated precursor obtained: the molar ratio of Li in the lithium compound is (100+2) { [ (50) +2 ]. Times.1.05 }, al (Si 2O5)2 -coated precursor and lithium hydroxide were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 880 ℃, the sintering time is 22 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 22:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: ferrous sulfate was dissolved in water to give a molar concentration of Fe ions of 2mol/L. The precipitant sodium phosphate was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: and adding the M solution and the precipitant solution into a reaction kettle dropwise according to the molar ratio of Fe in the M solution to sodium phosphate in the precipitant solution being 3:2. And nitrogen is introduced in the reaction process for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 400℃for 17 hours in an air atmosphere to prepare Al (Si 2O5)2. Fe in the precursor prepared in step 1 was then Fe in the precursor prepared Al (molar ratio of Al in Si 2O5)2 was 100:0.5), and the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
According to the 2 nd step [ the total amount of Fe+ coated Al (Al in Si 2O5)2) in the obtained Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound was (100+0.5) { [100+0.5 ]. Times.1.05 }, al (Si 2O5)2 coated precursor and lithium hydroxide) were weighed and mixed uniformly.
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in nitrogen atmosphere for calcination, wherein the sintering temperature is 1000 ℃ and the sintering time is 16 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 23:
Step 1, preparing a precursor:
preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in water, the molar ratio of Ni to Co to Mn is 1:1:1, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added dropwise into a reaction kettle according to the molar ratio of the sodium hydroxide in the precipitant solution of (Ni+Co+Mn) in the M solution of 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.0, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 750℃for 14 hours in an air atmosphere to prepare Al (Si 2O5)2. Then (Ni+Co+Mn) in the precursor prepared in step 1, the molar ratio of Al in Si 2O5)2 was 100:2, and the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the molar ratio of Li in the lithium compound of (100+2): { [ (100) +2 ]. Times.1.05 } in the Al (Si 2O5)2) -coated precursor obtained (Ni+Co+Mn) +coated Al (Si 2O5)2).
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an air atmosphere for calcination, wherein the sintering temperature is 880 ℃, the sintering time is 17 hours, and naturally cooling to room temperature after the sintering is finished, so that the obtained material is the LiAlSi 4O10 coated lithium ion battery anode material.
Example 24:
Step 1, preparing a precursor:
Preparing an M solution and a precipitant solution: nickel sulfate, cobalt sulfate and aluminum sulfate are dissolved in water, the molar ratio of Ni to Co to Al is 0.8:0.15:0.05, and the total molar concentration of metal ions is 2mol/L. The precipitant sodium hydroxide was dissolved in water to a molar concentration of 2mol/L.
Precipitation reaction: the M solution and the precipitant solution are added into a reaction kettle dropwise according to the molar ratio of the sodium hydroxide in the precipitant solution of (Ni+Co+Al) in the M solution of 1:2. In the reaction process, the pH buffer is utilized to regulate the pH of the mixed solution to about 11.8, and meanwhile, nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, separating, and drying to obtain a precursor for later use;
Step 2, oxide coating:
The silica and alumina were weighed according to a mole ratio of Si in the silica to Al in the alumina of 4:1. The mixture was uniformly mixed and then calcined at 750℃for 14 hours in an air atmosphere to prepare Al (Si 2O5)2. Then, in the precursor prepared in step 1, (Ni+Co+Al) the molar ratio of Al in the prepared Al (Si 2O5)2) was 100:2, the precursor and Al (Si 2O5)2) were weighed and uniformly mixed.
Step 3, lithiation:
The Al (Si 2O5)2) -coated precursor and lithium hydroxide were weighed and mixed uniformly according to the molar ratio of Li in the lithium compound of (100+2): { [ (100) +2 ]. Times.1.05 } in the Al (Si 2O5)2) -coated precursor obtained (Ni+Co+Al) +coated Al (Si 2O5)2).
And (3) placing the precursor coated by the Al (Si 2O5)2) mixed with the lithium compound in an oxygen atmosphere for calcination, wherein the sintering temperature is 750 ℃, and the sintering time is 17 hours.
Example 25:
Step 1, preparation of the precursor, preparation steps were as in example 24:
step 2, preparing a positive electrode material:
The precursor and lithium hydroxide are weighed and mixed uniformly according to the mole ratio of (Ni+Co+Al) in the precursor obtained in step 1, wherein Li in the lithium hydroxide is 100: [ (100). Times.1.05 ]. The precursor of the well-mixed lithium compound was calcined at 700 c for 12 hours in an oxygen atmosphere. And after sintering, naturally cooling to room temperature, and obtaining the material, namely the lithium ion battery anode material.
Step 3, preparing Al (Si 2O5)2:
The mixture was uniformly mixed in a molar ratio of Al to Si in the oxidation of aluminum hydroxide of 1:4 and then calcined at 500℃for 4 hours in an oxygen atmosphere to prepare Al (Si 2O5)2).
Step 4, coating LiAlSi 4O10 on the positive electrode material of the lithium ion battery:
And (3) according to the (Ni+Co+Al) Al (the molar ratio of Al in Si 2O5)2 to Li in the lithium compound is 100:1:1) in the positive electrode material prepared in the step 2, uniformly mixing, then placing the mixture in an oxygen atmosphere, calcining for 2 hours at 500 ℃, and naturally cooling to room temperature after sintering is finished, wherein the obtained material is the lithium ion battery positive electrode material coated with LiAlSi 4O10.
Example 26:
Step 1, preparation of the precursor, preparation steps were as in example 24:
step 2, preparing a positive electrode material:
The precursor and lithium hydroxide are weighed and mixed uniformly according to the mole ratio of (Ni+Co+Al) in the precursor obtained in step 1, wherein Li in the lithium hydroxide is 100: [ (100). Times.1.05 ]. The precursor of the well-mixed lithium compound was calcined at 700 c for 12 hours in an oxygen atmosphere. And after sintering, naturally cooling to room temperature, and obtaining the material, namely the lithium ion battery anode material.
Step 3, preparing Al (Si 2O5)2:
The mixture was uniformly mixed in a molar ratio of Al to Si in the oxidation of aluminum hydroxide of 1:4 and then calcined at 500℃for 4 hours in an oxygen atmosphere to prepare Al (Si 2O5)2).
Step 4, coating LiAlSi 4O10 on the positive electrode material of the lithium ion battery:
And (3) according to the (Ni+Co+Al) Al (Al in Si 2O5)2: li in the lithium compound: mg in the doped MgO in the molar ratio of 100:1:1:0.1 in the positive electrode material prepared in the step 2, uniformly mixing, then placing the mixture in an oxygen atmosphere, calcining at 700 ℃ for 2 hours, naturally cooling to room temperature after sintering is finished, and obtaining the material which is the lithium ion battery positive electrode material coated by LiAlSi 4O10.
Example 27:
step 1, preparation of Al (Si 2O5)2:
According to Al in aluminum hydroxide: the molar ratio of Si in the oxidation was 1:4, and after mixing them uniformly, it was calcined at 500 ℃ in an oxygen atmosphere for 4 hours to prepare Al (Si 2O5)2.
Step 4, coating LiAlSi 4O10 on the positive electrode material of the lithium ion battery:
And (3) according to the molar ratio of (Ni+Co+Mn) to Al (Al in Si 2O5)2 to Li in lithium compound) in the purchased positive electrode material being 100:1:1, uniformly mixing, then placing the mixture in an oxygen atmosphere at 500 ℃ for calcining for 2 hours, and naturally cooling to room temperature after sintering is finished, thus obtaining the material which is the LiAlSi 4O10 coated positive electrode material of the lithium ion battery.
Claims (12)
1. The LiAlSi 4O10 -coated lithium ion battery anode material is characterized in that an intermediate Al (Si 2O5)2) is used for coating the lithium ion battery anode material with LiAlSi 4O10 by adopting a solid phase synthesis method, and the lithium ion battery anode material is layered oxide, lithium-rich manganese-based oxide, olivine-type lithium iron phosphate or spinel-type lithium manganate.
2. The method for preparing the LiAlSi 4O10 coated lithium ion battery positive electrode material as claimed in claim 1, wherein an in-situ coating method is adopted, and the method comprises the following steps:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to ensure that the total molar concentration of M ions is more than or equal to 1mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the solution M and the precipitant solution, stirring at the same time, controlling the reaction temperature to be 30-85 ℃ for 10-48 hours, regulating the pH value of the solution to be 8-12 by using a pH regulator in the reaction process, introducing a protective gas which is nitrogen, argon or carbon dioxide when regulating the pH value, centrifuging or suction-filtering the precipitate obtained by the reaction, and drying to obtain a precursor;
(2) Coating oxide by hydrolysis method or mixing method:
Adopts a hydrolysis method:
Weighing the precursor, the ethyl orthosilicate and the aluminum isopropoxide according to the molar ratio of M in the ethyl orthosilicate to Si in the aluminum isopropoxide of 100 to alpha to beta, wherein 0.4< alpha <10,0.1< beta <2.5; dispersing/dissolving the weighed precursor, tetraethoxysilane and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100 epsilon to delta, 2 epsilon <2000,0.02< delta <0.5, and carrying out suction filtration and drying to obtain powder; calcining the powder in an air atmosphere, an oxygen atmosphere or a nitrogen atmosphere at 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si 2O5)2 -coated precursor), wherein the precipitant in the step (1) is in the nitrogen atmosphere when the precipitant is phosphate, and the rest is oxygen, air or nitrogen;
or a mixing method is adopted:
Weighing the silicon oxide, silicate or silicon-containing organic matter and aluminum oxide or salt according to the mole ratio of Si to Al in the silicon oxide, silicate or silicon-containing organic matter to Al in the aluminum oxide or salt of 4:1; uniformly mixing weighed matters, calcining in oxygen or air atmosphere to prepare Al (Si 2O5)2, wherein the calcining temperature is 300-1100 ℃ and the calcining time is 0.5-18 hours, and weighing the precursor and Al (Si 2O5)2) according to the M in the precursor, wherein the molar ratio of Al in the precursor to Al (Si 2O5)2 is 100:beta, 0.1< beta <2.5, and the mixture of Al (Si 2O5)2 and the precursor is obtained;
(3) Lithiation treatment was performed on a mixture of Al (Si 2O5)2 and precursor:
(3-1) mixing Al (mixture of Si 2O5)2 and precursor) with a lithium compound by any one of the following methods:
The first method is as follows:
For layered oxides and lithium iron phosphate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: li in lithium compound is (100+beta) [ (100+beta) ×1.05], and uniformly mixing the weighed substances to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100 corresponds to M in the precursor, is the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, beta corresponds to Al (Al in Si 2O5)2, is the theoretical lithium amount of the Al (Si 2O5)2 converted into LiAlSi 4O10, and is more than 5% of lithium to supplement the volatilized lithium amount when 1.05 is sintered at high temperature), and 0.1< beta <2.5;
The second method is as follows:
For lithium-rich manganese-based oxides: according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor: the molar ratio of Li in the lithium compound is (100+beta) { [ (100+pi) +beta ]. Times.1.05 }, weighing the Al (Si 2O5)2 coated precursor and the lithium compound, and uniformly mixing the weighed matters to obtain Al (Si 2O5)2/precursor mixture) of the well-mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, and beta corresponds to the theoretical lithium amount of Al (Al in Si 2O5)2, al (Si 2O5)2 converted into LiAlSi 4O10, and 1.05 is the theoretical lithium amount required to be added by 5% during high-temperature sintering to supplement volatilized lithium, pi is more than or equal to 100, and 0.1< beta is less than 2.5;
The third method is as follows:
For lithium manganate: weighing Al (Si 2O5)2 coated precursor and lithium compound according to the molar ratio of M+ coated Al (total amount of Al in Si 2O5)2) in the Al (Si 2O5)2 coated precursor being (100+beta): [ (50+beta). Times.1.05 ], and uniformly mixing to obtain Al (Si 2O5)2/precursor mixture of the lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate), 100 corresponds to M in the precursor, beta corresponds to Al (Al in Si 2O5)2, theoretical lithium amount of the Al converted into LiAlSi 4O10 is Al (Si 2O5)2), and 1.05 is the lithium amount required to be added by 5% during high-temperature sintering to supplement the volatilized lithium amount, and 0.1< beta <2.5;
and (3-2) calcining the Al (Si 2O5)2/precursor mixture of the lithium compound in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain the LiAlSi 4O10 coated lithium ion battery anode material.
3. The method for preparing a positive electrode material for a lithium ion battery according to claim 2, wherein when M is a metal, the metal is one or more of Ni, co, mn, al, fe, ti, zr, mg, V, nb, ga, sn, sc, cu, la, ca, Y, mo, zn, cr, ce.
4. The method for preparing a positive electrode material for a lithium ion battery according to claim 2, wherein the soluble salt of M is sulfate, nitrate, acetate, sulfite or nitrite.
5. The method for preparing a positive electrode material for a lithium ion battery according to claim 2, wherein the precipitant is one or more of oxalate, carbonate, hydroxide and phosphate.
6. The method for preparing a positive electrode material of a lithium ion battery according to claim 2, wherein the alcohol is one or more of ethanol, propanol, isopropanol and butanol; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, tartaric acid and oxalic acid.
7. The method for preparing a positive electrode material for a lithium ion battery according to claim 2, wherein the lithium compound is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium nitrate.
8. The method for preparing the LiAlSi 4O10 coated lithium ion battery cathode material according to claim 1, wherein an ex-situ coating method is adopted, comprising the following steps:
(1) Preparing a precursor:
(1-1) preparing M solution and precipitant solution: dissolving soluble salt of M in water to make the total molar concentration of M ions be more than or equal to 1mol/L, and dissolving precipitant in water to make the molar concentration of precipitant be more than or equal to 1mol/L; m is one or more of metal, si or B;
(1-2) precipitation reaction: mixing the solution M and the precipitant solution, stirring, controlling the temperature to be 30-85 ℃ during the reaction, controlling the reaction time to be 10-48 hours, regulating the pH value of the solution to be 8-12 by using a pH regulator during the reaction, introducing a protective gas which is nitrogen, argon or carbon dioxide during the regulation of the pH value, centrifuging or filtering and separating the precipitate obtained by the reaction, and drying to obtain a precursor;
(2) Preparing a positive electrode material:
(2-1) mixing the precursor with a lithium compound by any one of the following methods:
The first method is as follows:
For conventional layered oxides and lithium iron phosphate: according to the molar ratio of Li in the lithium compound in the precursor being 100 [ (100) multiplied by 1.05], weighing the precursor and the lithium compound, and uniformly mixing the weighed matters to obtain the precursor of the well mixed lithium compound, wherein 100 corresponds to M in the precursor, namely the theoretical lithium amount of the precursor converted into the traditional layered oxide and lithium iron phosphate, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount during high-temperature sintering;
The second method is as follows:
For lithium-rich manganese-based oxides: the molar ratio of Li in the lithium compound in the precursor obtained in the step 1 is 100 [ (100+pi) ×1.05], the precursor and the lithium compound are weighed and uniformly mixed to obtain the precursor of the well mixed lithium compound, wherein 100+pi corresponds to the theoretical lithium amount of the precursor converted into the lithium-rich manganese-based oxide, 100 corresponds to M in the precursor, and more than 5% of lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering, and pi is more than or equal to 0 and less than or equal to 100;
The third method is as follows:
And (2) for lithium manganate, according to the molar ratio of M in the lithium compound in the precursor obtained in the step (1) being 100, (50 multiplied by 1.05), weighing the precursor and the lithium compound, and uniformly mixing the precursor and the lithium compound to obtain the precursor of the well mixed lithium compound, wherein 50 is the theoretical lithium amount of the precursor converted into lithium manganate, 100 corresponds to M in the precursor, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount when sintering at high temperature;
(2-2) placing the precursor of the mixed lithium compound in air, oxygen or nitrogen atmosphere for calcination, wherein the sintering temperature is 600-1200 ℃, the sintering time is 5-22 hours, and cooling to room temperature to obtain the lithium ion battery anode material;
(3) Preparation of Al (Si 2O5)2:
Weighing raw materials according to the mole ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matters of 1:4, uniformly mixing the weighed materials, calcining in oxygen or air atmosphere at the calcining temperature of 300-1100 ℃ for 0.5-18 hours to obtain Al (Si 2O5)2;
(4) Coating LiAlSi 4O10 on a lithium ion battery anode material:
Weighing raw materials according to the molar ratio of M to Al (Al in Si 2O5)2 to Li in a lithium compound) of 100 to beta in the positive electrode material or the purchased positive electrode material, uniformly mixing the weighed materials, wherein beta is 0.1 to 2.5, calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5 to 6 hours, calcining at 300 to 700 ℃, and naturally cooling to room temperature to obtain the lithium ion battery positive electrode material coated by LiAlSi 4O10.
9. The method for preparing a positive electrode material for a lithium ion battery according to claim 8, wherein when M is a metal, the metal is one or more of Ni, co, mn, al, fe, ti, zr, mg, V, nb, ga, sn, sc, cu, la, ca, Y, mo, zn, cr, ce.
10. The method for preparing a positive electrode material for a lithium ion battery according to claim 8, wherein the soluble salt of M is sulfate, nitrate, acetate, sulfite or nitrite.
11. The method for preparing a positive electrode material of a lithium ion battery according to claim 8, wherein the precipitant is one or more of oxalate, carbonate, hydroxide and phosphate.
12. The method for preparing a positive electrode material of a lithium ion battery according to claim 8, wherein the lithium compound is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium nitrate.
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