CN114023962A - LiAlSi4O10Coated lithium ion battery anode material and preparation method thereof - Google Patents
LiAlSi4O10Coated lithium ion battery anode material and preparation method thereof Download PDFInfo
- Publication number
- CN114023962A CN114023962A CN202111214987.3A CN202111214987A CN114023962A CN 114023962 A CN114023962 A CN 114023962A CN 202111214987 A CN202111214987 A CN 202111214987A CN 114023962 A CN114023962 A CN 114023962A
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- Prior art keywords
- lithium
- precursor
- coated
- molar ratio
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 108
- 239000010405 anode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 229910052670 petalite Inorganic materials 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910010100 LiAlSi Inorganic materials 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims description 350
- 229910003002 lithium salt Inorganic materials 0.000 claims description 112
- 159000000002 lithium salts Chemical class 0.000 claims description 112
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 110
- 229910052744 lithium Inorganic materials 0.000 claims description 110
- 229910052751 metal Inorganic materials 0.000 claims description 95
- 239000002184 metal Substances 0.000 claims description 95
- 238000002156 mixing Methods 0.000 claims description 95
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 93
- 239000011572 manganese Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 238000001354 calcination Methods 0.000 claims description 70
- 238000005245 sintering Methods 0.000 claims description 64
- 239000003570 air Substances 0.000 claims description 55
- 239000012298 atmosphere Substances 0.000 claims description 54
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 claims description 44
- 239000010406 cathode material Substances 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 38
- 239000001301 oxygen Substances 0.000 claims description 38
- 229910052760 oxygen Inorganic materials 0.000 claims description 38
- 238000005303 weighing Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 28
- 238000006138 lithiation reaction Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 26
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 230000001105 regulatory effect Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013589 supplement Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 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
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 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
- 230000001681 protective effect Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010703 silicon Substances 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
- 230000001276 controlling effect Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 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
- 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-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
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 238000011066 ex-situ storage Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- 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
- 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
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 162
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 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
- 239000011259 mixed solution Substances 0.000 description 9
- 239000006179 pH buffering agent Substances 0.000 description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 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
- 150000002500 ions Chemical class 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 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
- 230000037427 ion transport Effects 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- 150000002826 nitrites Chemical class 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Images
Classifications
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- 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
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Abstract
The invention belongs to the technical field of battery materials, and particularly relates to LiAlSi4O10A coated lithium ion battery anode material and a preparation method thereof. The invention carries out fast lithium ion conductor LiAlSi on lithium ion battery anode materials with different crystal structures by an in-situ and non-in-situ chemical synthesis method4O10And (4) coating. The lithium ion battery anode material prepared by the preparation method 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, good product uniformity and suitability for gaugesAnd (5) molding production. The 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.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to LiAlSi4O10A coated lithium ion battery anode material and a preparation method thereof.
Background
The popularization of lithium ion battery electric vehicles is an energy reform promoted by the nation, and is a key link for realizing 'carbon peak reaching' and 'carbon neutralization'. The core of the electric automobile is a battery, and the key of the battery is the positive pole. The problems of slow interface lithium ion transmission and poor interface stability of the conventional anode material generally exist. For liquid batteries, interfacial lithium ion transport slowly limits the rate of charge and discharge of the positive electrode material at high current densities and the realization of power density and fast charging of lithium ion batteries. Meanwhile, under high voltage, the surface of the high-activity anode material can generate side reaction with electrolyte to generate gas and increase the impedance of the battery. For solid-state batteries, the rate of lithium ion transport and interfacial stability between the positive electrode materials and the solid-state electrolyte largely determine the performance of the battery. The problems of slow interfacial lithium ion transport and poor interfacial stability of the cathode material significantly limit the further development of liquid and solid batteries. Currently, the main strategies to ameliorate the above problems are bulk doping and surface coating. However, this problem is not well solved at present, since the improvement effects of the conventional bulk doping and surface coating are not satisfactory. Therefore, it is very important and urgent to develop a method capable of efficiently improving interfacial lithium ion transport and interfacial stability of the cathode material.
Disclosure of Invention
The present invention is to solve at least the above problems and provide a LiAlSi4O10The coated lithium ion battery anode material is prepared by carrying out fast lithium ion conductor LiAlSi on lithium ion battery anode materials with different crystal structures by an in-situ and non-in-situ chemical synthesis method4O10And (4) coating. Thereby improving the interfacial lithium ion diffusion coefficient, rate capability, interfacial stability and cycling stability of the lithium ion battery anode material.
In a first aspect of the present invention, a LiAlSi is provided4O10Coating the anode material of the lithium ion battery by using an intermediate product Al (Si)2O5)2The method adopts a solid-phase synthesis method to carry out LiAlSi on the anode material of the lithium ion battery4O10Coating; the anode material of the lithium ion battery is a layered oxide and rich lithiumManganese-based oxides, olivine-type lithium iron phosphate, or spinel-type lithium manganate.
In a second aspect of the invention, LiAlSi is provided using an in-situ coating method4O10The preparation method of the coated lithium ion battery anode material comprises the following steps:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1 mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing a metal solution and a precipitant solution, stirring simultaneously, controlling the reaction temperature to be 30-85 ℃, controlling the reaction temperature to be 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 when regulating the pH value, wherein the protective gas is nitrogen, argon or carbon dioxide, centrifuging or suction-filtering and separating precipitates obtained by the reaction, and drying to obtain a precursor;
(2) coating the oxide by a hydrolysis method or a mixing method:
adopting a hydrolysis method:
weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of M in the precursor to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100: alpha: beta, wherein the molar ratio is 0.4<α<10，0.1<β<2.5; dispersing/dissolving weighed precursors, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100: epsilon: delta, 2<ε<2000，0.02<δ<0.5, carrying out suction filtration and drying to obtain powder; calcining the powder in air atmosphere, oxygen atmosphere or nitrogen atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si)2O5)2The coated precursor is in a nitrogen atmosphere when the precipitator in the step (1) is phosphate, and oxygen or air or nitrogen is used in the rest cases;
or a mixing method is adopted:
according to the mol of Al in Si in oxide, silicate or silicon-containing organic matterWeighing oxide of silicon, silicate or organic matter containing silicon and oxide or salt of aluminum in a molar ratio of 4: 1; the weighed materials are evenly mixed and then calcined in the atmosphere of oxygen or air to prepare Al (Si)2O5)2The calcination temperature is 300-1100 ℃, and the calcination time is 0.5-18 hours; according to the precursor M, Al (Si) is prepared2O5)2The molar ratio of Al in the alloy is 100: beta, 0.1<β<2.5, weigh precursor and Al (Si)2O5)2And mixing the weighed materials uniformly to obtain Al (Si)2O5)2And a mixture of precursors;
(3) for Al (Si)2O5)2And carrying out lithiation treatment on the mixture of the precursor:
(3-1) to Al (Si)2O5)2And mixing the precursor mixture with lithium salt by any one of the following methods:
the first method comprises the following steps:
for the layered oxide and lithium iron phosphate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (100+ beta). times.1.05]Weighing Al (Si)2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 100 corresponds to M in the precursor, theoretical amount of lithium for the conversion of the precursor into a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, and 0.1<β<2.5；
The second method comprises the following steps:
for lithium-rich manganese-based oxides: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2Of Al in (1)The molar ratio of Li in the lithium salt is (100+ beta) { [ (100+ pi) + beta { (100+ beta) } in total]X 1.05} and Al (Si) was weighed2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2A mixture of precursors, where 100+ pi corresponds to the theoretical amount of lithium converted from the precursor to a lithium-rich manganese-based oxide, 100 corresponds to M in the precursor, the theoretical amount of lithium converted from the precursor to a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) (Si2O5)2Al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5 percent of lithium is needed to be added to supplement the amount of the volatilized lithium during high-temperature sintering, pi is more than or equal to 0 and less than or equal to 100, and 0.1<β<2.5；
The third method comprises the following steps:
for lithium manganate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (50+ beta). times.1.05]Weighing Al (Si)2O5)2The coated precursor and lithium salt are evenly mixed to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 50 is the theoretical amount of lithium converted from precursor to lithium manganate, 100 corresponds to M in precursor, the theoretical amount of lithium converted from precursor to conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, and 0.1<β<2.5；
(3-2) mixing the lithium salt with Al (Si)2O5)2Calcining the precursor mixture in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Third aspect of the inventionIn one aspect, LiAlSi using ex-situ coating methods is also presented4O10The preparation method of the coated lithium ion battery anode material comprises the following steps:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1mol/L, and dissolving a precipitant in water to make the molar concentration of the precipitant more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing a metal solution and a precipitant solution, stirring, controlling the temperature to be 30-85 ℃ during 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 when regulating the pH value, wherein the protective gas is nitrogen, argon or carbon dioxide, centrifuging or suction-filtering and separating precipitates obtained by the reaction, and drying to obtain a precursor;
(2) preparing a positive electrode material:
(2-1) mixing the precursors with lithium salt by any one of the following methods:
the first method comprises the following steps:
for conventional layered oxides and lithium iron phosphate: weighing a precursor and a lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor of 100 [ (100). times.1.05 ], and uniformly mixing the weighed substances to obtain the precursor of the well-mixed lithium salt, wherein 100 corresponds to M in the precursor, namely the precursor is converted into the theoretical lithium amount of the traditional layered oxide and lithium iron phosphate, and 5% more lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering;
the second method comprises the following steps:
for lithium-rich manganese-based oxides: weighing the precursor and the lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor obtained in the step 1 being 100: [ (100+ pi) × 1.05], and uniformly mixing the precursor and the lithium salt to obtain a precursor mixed with the lithium salt, 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, 5% more 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 comprises the following steps:
for lithium manganate, weighing the precursor and lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor obtained in the step 1 being 100 (50 x 1.05), and uniformly mixing the precursor and the lithium salt to obtain a precursor mixed with the lithium salt, wherein 50 is the theoretical lithium amount of the lithium manganate converted from the precursor, 100 corresponds to M in the precursor, and 5% more lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering;
(2-2) calcining the precursor mixed with the lithium salt in air, oxygen or nitrogen atmosphere at the sintering temperature of 600-1200 ℃ for 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 molar ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matter being 1:4, uniformly mixing the weighed materials, calcining in an oxygen or air atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to prepare Al (Si)2O5)2；
(4) Coating LiAlSi on the anode material of the lithium ion battery4O10：
According to M: Al (Si) in the cathode material (or purchased cathode material)2O5)2Weighing raw materials with the molar ratio of Al to Li in lithium salt of 100: beta, and uniformly mixing the weighed materials, wherein the molar ratio of Al to Li in lithium salt is 0.1<β<2.5; calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5-6 hours at 300-700 ℃, and naturally cooling to room temperature to obtain the LiAlSi4O10And (3) a coated lithium ion battery cathode material.
LiAlSi prepared by the method of the invention4O10The coated lithium ion battery anode material 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, and capability of obtaining the productHas the advantages of large yield, good result repeatability and the like.
In some embodiments, the method for preparing the lithium ion battery cathode material is characterized in that the metal M 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, and B.
In some embodiments, the soluble salt of the metal M is a sulfate, nitrate, acetate, sulfite, or nitrite salt.
In some embodiments, the precipitating agent is one or more of an oxalate, a carbonate, a hydroxide, and a 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 salt is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, and lithium nitrate.
According to the preparation method provided by the embodiment of the invention, the lithium ion conductor LiAlSi is used for carrying out fast lithium ion on the lithium ion battery anode materials with different crystal structures by an in-situ and non-in-situ chemical synthesis method4O10And (4) coating. Thereby improving the interfacial lithium ion diffusion coefficient, rate capability, interfacial stability and cycling stability of the lithium ion battery anode material. 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 easily obtained reaction raw materials, no toxicity, low cost, no need of special protection in the production process, easily controlled 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 obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is an XRD pattern of a positive electrode material for a lithium ion battery, wherein (a) is LiAlSi prepared in example 1 of the present invention4O10The XRD pattern of the coated lithium ion battery anode material, and (b) is the XRD pattern of the unmodified lithium ion battery anode material.
In FIG. 2, (a) is LiAlSi prepared in example 1 of the present invention4O10The discharge specific capacity cycle schematic diagram of the coated lithium ion battery anode material under the conditions of 1C (250mA/g) and 4.8V cut-off voltage, and (b) the discharge specific capacity cycle schematic diagram of the unmodified lithium ion battery anode material under the conditions of 1C (250mA/g) and 4.8V cut-off voltage.
FIG. 3 shows LiAlSi prepared in example 1 of the present invention4O10And the multiplying power comparison graph of the coated lithium ion battery anode material and the unmodified lithium ion battery anode material.
FIG. 4 is LiAlSi prepared according to an embodiment of the present invention4O10And comparing the impedance spectrum of the coated lithium ion battery anode material with that of an unmodified lithium ion battery anode material.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, and the embodiments described below with reference to the accompanying drawings are exemplary and intended to be illustrative of the present invention and should not be construed as limiting the present invention.
The embodiment of the invention provides LiAlSi4O10Coating the anode material of the lithium ion battery by using an intermediate product Al (Si)2O5)2The method adopts a solid-phase synthesis method to carry out LiAlSi on lithium ion battery anode materials with different crystal structures4O10Coating; the anode material of the lithium ion battery is a layered oxide, a lithium-rich manganese-based oxide, olivine lithium iron phosphate or spinel lithium manganate.
LiAlSi prepared according to the embodiment of the invention4O10Compared with the unmodified lithium ion battery anode material, the coated lithium ion battery anode material has the advantages that the interfacial lithium ion diffusion coefficient, the rate capability, the interfacial stability and the cycle stability are obviously improved.
The embodiment of the invention also provides LiAlSi4O10The preparation method of the coated lithium ion battery anode material adopts an in-situ coating method and comprises the following steps:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1 mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing the metal solution and the precipitant solution, and adding the mixture into a reaction kettle dropwise, or adding the precipitant solution into the reaction kettle containing the metal solution dropwise, or adding the metal solution into the reaction kettle containing the precipitant solution dropwise while stirring. In the reaction process, a pH regulator can be used for regulating the pH value of the solution to be 8-12, protective gas is introduced when the pH value is regulated, the protective gas is nitrogen, argon or carbon dioxide, the temperature is controlled to be 30-85 ℃ during the reaction, the time is 10-48 hours, the precipitate obtained by the reaction is centrifuged or filtered, and the precursor is obtained after drying;
(2) coating the oxide by a hydrolysis method or a mixing method:
adopting a hydrolysis method:
weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of M in the precursor (or M in the purchased precursor) to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100: alpha: beta, wherein the molar ratio is 0.4<α<10，0.1<β<2.5; dispersing/dissolving weighed precursors, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100: epsilon: delta, 2<ε<2000，0.02<δ<0.5, carrying out suction filtration and drying to obtain powder; subjecting the powder to an air atmosphere, an oxygen atmosphere orCalcining in nitrogen atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si)2O5)2The coated precursor is in a nitrogen atmosphere when the precipitator in the step (1) is phosphate, and oxygen or air or nitrogen is used in the rest cases;
or a mixing method is adopted:
weighing silicon oxide, silicate or silicon-containing organic matter and aluminum oxide or salt according to the molar ratio of Si to Al in the silicon oxide, silicate or silicon-containing organic matter to be 4: 1; the weighed materials are evenly mixed and then calcined in the atmosphere of oxygen or air to prepare Al (Si)2O5)2The calcination temperature is 300-1100 ℃, and the calcination time is 0.5-18 hours; according to M in the precursor (or M in the purchased precursor), preparing the obtained Al (Si)2O5)2The molar ratio of Al in the alloy is 100: beta, 0.1<β<2.5, weigh precursor and Al (Si)2O5)2And mixing the weighed materials uniformly to obtain Al (Si)2O5)2And a mixture of precursors;
(3) for Al (Si)2O5)2And carrying out lithiation treatment on the mixture of the precursor:
(3-1) to Al (Si)2O5)2And mixing the precursor mixture with lithium salt by any one of the following methods:
the first method comprises the following steps:
for conventional layered oxides and lithium iron phosphate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (100+ beta). times.1.05]Weighing Al (Si)2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 100 corresponds to M in the precursor, theoretical amount of lithium for the conversion of the precursor into a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, and 0.1<β<2.5；
The second method comprises the following steps:
for lithium-rich manganese-based oxides: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta) { [ (100+ pi) + beta]X 1.05} and Al (Si) was weighed2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2A mixture of precursors, where 100+ pi corresponds to the theoretical amount of lithium converted from the precursor to a lithium-rich manganese-based oxide, 100 corresponds to M in the precursor, the theoretical amount of lithium converted from the precursor to a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) (Si2O5)2Al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5 percent of lithium is needed to be added to supplement the amount of the volatilized lithium during high-temperature sintering, pi is more than or equal to 0 and less than or equal to 100, and 0.1<β<2.5；
The third method comprises the following steps:
for lithium manganate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (50+ beta). times.1.05]Weighing Al (Si)2O5)2The coated precursor and lithium salt are evenly mixed to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 50 is the theoretical amount of lithium converted from precursor to lithium manganate, 100 corresponds to M in precursor, the theoretical amount of lithium converted from precursor to conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O10Theoretical lithium of1.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, 0.1<β<2.5；
(3-2) mixing the lithium salt with Al (Si)2O5)2Calcining the precursor mixture in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain LiAlSi4O10And (3) a coated lithium ion battery cathode material.
The embodiment of the invention also provides another LiAlSi4O10The preparation method of the coated lithium ion battery anode material adopts an ex-situ coating method, and comprises the following steps:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1mol/L, and dissolving a precipitant in water to make the molar concentration of the precipitant more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing a metal solution and a precipitant solution, dropwise adding the metal solution and the precipitant solution into a reaction kettle together, or dropwise adding the precipitant solution into the reaction kettle containing the metal solution, or dropwise adding the metal solution into the reaction kettle containing the precipitant solution while stirring, regulating the pH value of the solution to be 8-12 by using a pH regulator in the reaction process, introducing a protective gas when regulating the pH value, wherein the protective gas is nitrogen, argon or carbon dioxide, controlling the temperature to be 30-85 ℃ during reaction, and the time to be 10-48 hours, centrifuging or performing suction filtration separation on precipitates obtained by the reaction, and drying to obtain a precursor;
(2) preparing a positive electrode material:
(2-1) mixing the precursors with lithium salt by any one of the following methods:
the first method comprises the following steps:
for conventional layered oxides and lithium iron phosphate: weighing a precursor and a lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor of 100 [ (100). times.1.05 ], and uniformly mixing the weighed substances to obtain the precursor of the well-mixed lithium salt, wherein 100 corresponds to M in the precursor and is the theoretical lithium amount of the precursor converted into the traditional layered oxide and the lithium iron phosphate, and 5% more lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering;
the second method comprises the following steps:
for lithium-rich manganese-based oxides: weighing the precursor and the lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor obtained in the step 1, wherein the molar ratio of M to Li in the lithium salt is 100 [ (100+ pi). times.1.05 ], uniformly mixing the precursor and the lithium salt to obtain a precursor of the well-mixed lithium salt, 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 is also the theoretical lithium amount of the precursor converted into the traditional layered oxide and the lithium iron phosphate, 5% more lithium is needed to be added 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 comprises the following steps:
for lithium manganate, weighing the precursor and lithium salt according to the molar ratio of M in the precursor obtained in the step 1 to Li in the lithium salt being 100 (50 x 1.05), and uniformly mixing the precursor and the lithium salt to obtain a precursor mixed with the lithium salt, wherein 50 is the theoretical lithium amount of the lithium manganate converted from the precursor, 100 corresponds to M in the precursor and is also the theoretical lithium amount of the traditional layered oxide and lithium iron phosphate converted from the precursor, and 1.05 is obtained by adding 5% more lithium to supplement the volatilized lithium amount during high-temperature sintering;
(2-2) calcining the precursor mixed with the lithium salt in air, oxygen or nitrogen atmosphere at the sintering temperature of 600-1200 ℃ for 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 molar ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matter being 1:4, uniformly mixing the weighed materials, calcining in an oxygen or air atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to prepare Al (Si)2O5)2；
(4) Coating LiAlSi on the anode material of the lithium ion battery4O10：
According to M: Al (Si) in the cathode material (or purchased cathode material)2O5)2Weighing raw materials with the molar ratio of Al to Li in lithium salt of 100: beta, and uniformly mixing the weighed materials, wherein the molar ratio of Al to Li in lithium salt is 0.1<β<2.5; calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5-6 hours at 300-700 ℃, and naturally cooling to room temperature to obtain the LiAlSi4O10And (3) a coated lithium ion battery cathode material.
In some embodiments, the metal M 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 the metal M is a sulfate, nitrate, acetate, sulfite, or nitrite salt.
In some embodiments, the precipitating agent is one or more of an oxalate, a carbonate, a hydroxide, and a 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 salt is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, and lithium nitrate.
According to the embodiment of the invention, the LiAlSi provided by the invention4O10The preparation method of the 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 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.
The following examples will be directed to LiAlSi4O10The preparation method of the coated lithium ion battery anode material is further explained in detail.
Example 1:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2 mol/L.
Precipitation reaction: and (3) dropwise adding the metal solution and the precipitant solution into the reaction kettle together according to the molar ratio of (Ni + Mn) in the metal solution to oxalic acid in the precipitant solution being 1:1. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
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 to Si in the tetraethoxysilane to Al in the aluminum isopropoxide of 100:0.8: 0.2. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of ethanol, deionized water and ammonia water according to the molar ratio of 100:10: 0.1. The reaction is carried out for 2.5 hours under the condition of heating and stirring at the temperature of 40 ℃ in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 500 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.2) { [ (100+25) +0.2 { (100+25)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 900 ℃ for 12 hours. After sintering, naturally cooling to room temperature to obtainThe material is LiAlSi4O10And (3) a coated lithium ion battery cathode material.
FIG. 1 is an XRD pattern of a positive electrode material for a lithium ion battery, wherein (a) is LiAlSi prepared in example 1 of the present invention4O10The XRD pattern of the coated lithium ion battery anode material, and (b) is the XRD pattern of the unmodified lithium ion battery anode material.
In FIG. 2, (a) is LiAlSi prepared in example 1 of the present invention4O10The discharge specific capacity cycle schematic diagram of the coated lithium ion battery anode material under the conditions of 1C (250mA/g) and 4.8V cut-off voltage, and (b) the discharge specific capacity cycle schematic diagram of the unmodified lithium ion battery anode material under the conditions of 1C (250mA/g) and 4.8V cut-off voltage.
FIG. 3 shows LiAlSi prepared in example 1 of the present invention4O10And the multiplying power comparison graph of the coated lithium ion battery anode material and the unmodified lithium ion battery anode material.
FIG. 4 is LiAlSi prepared according to an embodiment of the present invention4O10And comparing the impedance spectrum of the coated lithium ion battery anode material with that of an unmodified lithium ion battery anode material.
Example 2:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to enable the molar ratio of Ni to Co to Mn to be 1:1:4 and enable the total metal ion molar concentration to be 2 mol/L. The precipitant sodium oxalate was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium oxalate in the precipitant solution of 1:1. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (2) weighing the precursor, the tetraethoxysilane and the aluminum isopropoxide according to the molar ratio of (Ni + Co + Mn) in the precursor prepared in the step 1 to Si in the tetraethoxysilane to Al in the aluminum isopropoxide of 100:2: 0.5. Weighing the precursor and tetraethoxysilaneAnd dispersing/dissolving the aluminum isopropoxide in a mixed solvent of isopropanol, deionized water and hydrochloric acid in a molar ratio of 100:15: 0.02. The reaction is carried out for 1 hour at the temperature of 70 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 600 ℃ for 10h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+25) +0.5 { (100+25)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 950 ℃ for 18 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 3:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to enable the molar ratio of Ni to Co to Mn to be 8:1:1 and enable the total metal ion molar concentration to be 2 mol/L. The precipitant sodium oxalate was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium oxalate in the precipitant solution of 1: 1.02. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (2) weighing the precursor, the tetraethoxysilane and the aluminum isopropoxide according to the molar ratio of (Ni + Co + Mn) in the precursor prepared in the step 1 to Si in the tetraethoxysilane to Al in the aluminum isopropoxide of 100:2: 0.5. Weighing the precursor,Dispersing/dissolving ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of isopropanol, deionized water and hydrochloric acid in a molar ratio of 100:15: 0.02. The reaction is carried out for 0.5 hour at the temperature of 90 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in nitrogen at 300 ℃ for 15h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+0) +0.5 { (100+0) }]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 4:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel nitrate, cobalt nitrate and manganese nitrate in water to ensure that the molar ratio of Ni to Co to Mn is 7:1.5:1.5, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: according to the molar ratio of (Ni + Co + Mn) in the metal solution to sodium hydroxide in the precipitant solution being 1:2, the metal solution and the precipitant solution are added into the reaction kettle together drop by drop. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.5 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
in the precursor prepared according to the step 1(Ni + Co + Mn) the molar ratio of Si in ethyl orthosilicate to Al in aluminum isopropoxide was 100:4:1, and the precursor, ethyl orthosilicate, and aluminum isopropoxide were weighed. Dispersing/dissolving weighed precursors, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of propanol, deionized water and hydrochloric acid in a molar ratio of 100:100: 0.02. Heating and stirring are carried out during the reaction process, the temperature is between 40 ℃, and the reaction is carried out for 16 hours. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 670 ℃ for 7h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+0) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 750 ℃ for 12 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 5:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution, namely dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1.1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution at a molar ratio of (Ni + Mn) in the metal solution to oxalic acid in the precipitant solution of 1: 1.03. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
in the precursor prepared according to the step 1, (Ni + Mn): ethyl orthosilicateThe molar ratio of Si in the ester to Al in the aluminum isopropoxide is 100:2:0.5, and the precursor, ethyl orthosilicate and aluminum isopropoxide are weighed. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of ethanol, deionized water and hydrochloric acid in a molar ratio of 100:200: 0.02. The reaction is carried out for 10 minutes by heating and stirring at the temperature of 55 ℃ in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in oxygen at 300 ℃ for 0.5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+22) +0.5 { (100+22)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 870 ℃ for 24 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 6:
step 1, preparing a precursor:
preparing metal solution and precipitant solution, dissolving cobalt acetate in water to make the molar concentration of Co ion be 1 mol/L. The precipitant sodium carbonate was dissolved in water to give a molar concentration of 1 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution at a molar ratio of Co in the metal solution to sodium carbonate in the precipitant solution of 1: 1.03. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
weighing the precursor, tetraethoxysilane, aluminum isopropoxide and Co according to the molar ratio of Co in the precursor prepared in the step 1 to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100:4:1,Aluminum isopropoxide. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of ethanol, deionized water and hydrochloric acid according to the molar ratio of 100:220: 0.1. The reaction is carried out for 0.5 hour at 45 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in oxygen at 300 ℃ for 0.5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Co + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+0) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 920 ℃ for 16 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 7:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: manganese sulfate was dissolved in water to give a Mn ion molar concentration of 1 mol/L. The precipitant sodium carbonate was dissolved in water to give a molar concentration of 1 mol/L.
Precipitation reaction: the precipitant solution was added dropwise to the metal solution in a molar ratio of Mn in the metal solution to sodium carbonate in the precipitant solution of 1: 1.01. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (3) weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of Mn in the precursor prepared in the step 1 to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100:4: 1. Dispersing/dissolving weighed precursor, ethyl orthosilicate and aluminum isopropoxide in ethanolDeionized water and hydrochloric acid in a mixed solvent with a molar ratio of 100:250: 0.1. Heating and stirring are carried out during the reaction process, the temperature is between 35 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in oxygen at 500 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Mn + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+100) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 800 ℃ for 18 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 8:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: manganese sulfate was dissolved in water to give a Mn ion molar concentration of 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of Mn to sodium hydroxide in the metal solution of 1:2 in total. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.3 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (3) weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of Mn in the precursor prepared in the step 1 to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100:8: 2. Weighing the precursor, ethyl orthosilicate and aluminum isopropoxideDispersing/dissolving in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:300: 1. The reaction is carried out for 1 hour at 85 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 1000 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Mn + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (50) +2 { (]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 850 ℃ for 20 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 9:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Mn) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.3 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
weighing the precursor (Ni + Mn) prepared in the step 1, wherein the molar ratio of Si in tetraethoxysilane to Al in aluminum isopropoxide is 100:8:2Ethyl orthosilicate and aluminum isopropoxide. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:300: 1. The reaction is carried out for 1 hour at 85 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 1000 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (50) +2 { (]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 880 ℃ for 22 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 10:
step 1, preparing a precursor:
preparing metal solution and precipitant solution, dissolving ferrous sulfate in water to make the Fe ion molar concentration be 2 mol/L. The precipitant sodium phosphate is dissolved in water to make the molar concentration 2 mol/L.
Precipitation reaction: and dropwise adding the metal solution and the precipitant solution into the reaction kettle according to the molar ratio of Fe in the metal solution to sodium phosphate in the precipitant solution being 3: 2. And introducing nitrogen for protection in the reaction process. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (3) weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of Fe in the precursor prepared in the step 1 to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100:2: 0.5.Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of butanol, deionized water and tartaric acid in a molar ratio of 100:500: 1. The reaction is carried out for 2 hours under the temperature of 65 ℃ by heating and stirring in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in nitrogen at 400 ℃ for 12h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Fe + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [100+0.5 ]]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in a nitrogen atmosphere at 1000 ℃ for 16 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 11:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Co to Mn is 1:1:1, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.0 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
the precursor prepared according to step 1In the precursor (Ni + Co + Mn), the molar ratio of Si in the ethyl orthosilicate to Al in the aluminum isopropoxide is 100:10:2.5, and the precursor, the ethyl orthosilicate and the aluminum isopropoxide are weighed. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:2000: 0.02. The reaction is carried out for 4 hours under the condition of heating and stirring at the temperature of 35 ℃ in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 400 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (100) +2 { (100)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 880 ℃ for 17 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 12:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and aluminum sulfate in water to ensure that the molar ratio of Ni to Co to Al is 0.8:0.15:0.05, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Co + Al) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.8 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
and (2) weighing the precursor, the tetraethoxysilane and the aluminum isopropoxide according to the molar ratio of (Ni + Co + Al) in the precursor prepared in the step 1 to Si in the tetraethoxysilane to Al in the aluminum isopropoxide of 100:10: 2.5. Dispersing/dissolving the weighed precursor, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent of butanol, deionized water and oxalic acid in a molar ratio of 100:2000: 0.02. The reaction is carried out for 4 hours under the condition of heating and stirring at the temperature of 35 ℃ in the reaction process. After the reaction is finished, the mixture is filtered and dried. Calcining the obtained powder in air at 400 ℃ for 5h to obtain an intermediate product Al (Si)2O5)2A coated precursor.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Al) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (100) +2 { (100)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 750 ℃ for 17 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 13:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution, namely dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2 mol/L.
Precipitation reaction: and (3) dropwise adding the metal solution and the precipitant solution into the reaction kettle together according to the molar ratio of (Ni + Mn) in the metal solution to oxalic acid in the precipitant solution being 1:1. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 800 deg.C for 5 hr in air atmosphere to prepare Al (Si)2O5)2. Then, in the precursor prepared in the step 1, (Ni + Mn): Al (Si) prepared2O5)2The molar ratio of Al in the alloy is 100:0.2, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.2) { [ (100+25) +0.2 { (100+25)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 900 ℃ for 12 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 14:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to enable the molar ratio of Ni to Co to Mn to be 1:1:4 and enable the total metal ion molar concentration to be 2 mol/L. The precipitant sodium oxalate was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium oxalate in the precipitant solution of 1:1. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 900 deg.C for 5 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the precursor prepared in the step 1, (Ni + Co + Mn): the prepared Al (Si)2O5)2The molar ratio of Al in the alloy is 100:0.5, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+25) +0.5 { (100+25)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 950 ℃ for 18 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 15:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to enable the molar ratio of Ni to Co to Mn to be 8:1:1 and enable the total metal ion molar concentration to be 2 mol/L. The precipitant sodium oxalate was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium oxalate in the precipitant solution of 1: 1.02. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
according to the mol ratio of Si in silicon dioxide to Al in aluminum ethoxide of 4:1, weighingSilica and aluminum ethoxide. Mixing them uniformly, calcining at 850 deg.C for 10 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the precursor prepared in the step 1, (Ni + Co + Mn): the prepared Al (Si)2O5)2The molar ratio of Al in the alloy is 100:0.5, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+0) +0.5 { (100+0) }]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 16:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel nitrate, cobalt nitrate and manganese nitrate in water to ensure that the molar ratio of Ni to Co to Mn is 7:1.5:1.5, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: according to the molar ratio of (Ni + Co + Mn) in the metal solution to sodium hydroxide in the precipitant solution being 1:2, the metal solution and the precipitant solution are added into the reaction kettle together drop by drop. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.5 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
according toThe molar ratio of Si in tetraethyl silicate to Al in aluminum ethoxide was 4:1, and tetraethyl silicate and aluminum ethoxide were weighed. Mixing them uniformly, calcining at 1000 deg.C for 12 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the precursor prepared in the step 1, (Ni + Co + Mn): the prepared Al (Si)2O5)2The molar ratio of Al in the alloy is 100:1, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+0) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 750 ℃ for 12 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 17:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1.1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant oxalic acid was dissolved in water to a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution at a molar ratio of (Ni + Mn) in the metal solution to oxalic acid in the precipitant solution of 1: 1.03. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
tetraethyl silicate and aluminum nitrate were weighed so that the molar ratio of Si in tetraethyl silicate to Al in aluminum nitrate was 4: 1. Mixing them togetherAfter being homogenized, the mixture was calcined at 1050 ℃ for 16 hours in an air atmosphere to prepare Al (Si)2O5)2. Then, in the precursor prepared in the step 1, (Ni + Mn): Al (Si) prepared2O5)2The molar ratio of Al in the alloy is 100:0.5, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [ (100+22) +0.5 { (100+22)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 870 ℃ for 24 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 18:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: cobalt acetate was dissolved in water to give a molar concentration of Co ions of 1 mol/L. The precipitant sodium carbonate was dissolved in water to give a molar concentration of 1 mol/L.
Precipitation reaction: the metal solution was added dropwise to the precipitant solution at a molar ratio of Co in the metal solution to sodium carbonate in the precipitant solution of 1: 1.03. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and aluminum nitrate were weighed so that the molar ratio of Si in silica to Al in aluminum nitrate was 4: 1. Mixing them uniformly, calcining at 800 deg.C for 18 hr in air atmosphere to prepare Al (Si)2O5)2. Then (Ni + Mn) in the precursor prepared in the step 1Al (Si) of (2)2O5)2The molar ratio of Al in the alloy is 100:1, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Co + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+0) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 920 ℃ for 16 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 19:
step 1, coating with oxide:
silica and aluminum nitrate were weighed so that the molar ratio of Si in silica to Al in aluminum nitrate was 4: 1. Mixing them uniformly, calcining at 800 deg.C for 18 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the Mn in the purchased manganese hydroxide precursor, preparing the obtained Al (Si)2O5)2The molar ratio of Al in the alloy is 100:1, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 2, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Mn + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+1) { [ (100+100) +1 { (100+1)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2The coated precursor is placed in the airCalcining in the atmosphere, wherein the sintering temperature is 800 ℃, and the sintering time is 18 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 20:
step 1, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 800 deg.C for 18 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the Mn in the purchased manganese hydroxide precursor, preparing the obtained Al (Si)2O5)2The molar ratio of Al in the alloy is 100:1, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 2, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Mn + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (50) +2 { (]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at the sintering temperature of 850 ℃ for 20 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 21:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Mn is 1:3, and simultaneously ensuring that the total metal ion molar concentration is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Mn) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.3 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 600 deg.C for 17 hr in air atmosphere to prepare Al (Si)2O5)2. Then, in the precursor prepared in the step 1, (Ni + Mn): Al (Si) prepared2O5)2The molar ratio of Al in the alloy is 100:2, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Mn) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (50) +2 { (]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 880 ℃ for 22 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 22:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving ferrous sulfate in water to ensure that the molar concentration of Fe ions is 2 mol/L. The precipitant sodium phosphate is dissolved in water to make the molar concentration 2 mol/L.
Precipitation reaction: and dropwise adding the metal solution and the precipitant solution into the reaction kettle according to the molar ratio of Fe in the metal solution to sodium phosphate in the precipitant solution being 3: 2. And introducing nitrogen for protection in the reaction process. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 400 deg.C for 17 hr in air atmosphere to prepare Al (Si)2O5)2. Then preparing Fe in the precursor obtained in the step 1, and preparing the obtained Al (Si)2O5)2The molar ratio of Al in the alloy is 100:0.5, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2Fe + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+0.5) { [100+0.5 ]]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in a nitrogen atmosphere at 1000 ℃ for 16 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 23:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to ensure that the molar ratio of Ni to Co to Mn is 1:1:1, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Co + Mn) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.0 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 750 deg.C for 14 hr in air atmosphere to prepare Al (Si)2O5)2. Then according to the precursor prepared in the step 1, (Ni + Co + Mn): the prepared Al (Si)2O5)2The molar ratio of Al in the alloy is 100:2, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Mn) + coated Al (Si) in the coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (100) +2 { (100)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an air atmosphere at 880 ℃ for 17 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 24:
step 1, preparing a precursor:
preparing a metal solution and a precipitant solution: dissolving nickel sulfate, cobalt sulfate and aluminum sulfate in water to ensure that the molar ratio of Ni to Co to Al is 0.8:0.15:0.05, and simultaneously ensuring that the molar concentration of total metal ions is 2 mol/L. The precipitant sodium hydroxide was dissolved in water to give a molar concentration of 2 mol/L.
Precipitation reaction: the metal solution and the precipitant solution were added dropwise to the reaction vessel in a molar ratio of (Ni + Co + Al) in the metal solution to sodium hydroxide in the precipitant solution of 1: 2. In the reaction process, the pH of the mixed solution is regulated and controlled to be about 11.8 by using a pH buffering agent, and nitrogen is introduced for protection. Centrifuging or filtering the generated precipitate, and drying to obtain a precursor for later use;
step 2, coating with oxide:
silica and alumina were weighed so that the molar ratio of Si in silica to Al in alumina was 4: 1. Mixing them uniformly, calcining at 750 deg.C for 14 hr in air atmosphere to prepare Al (Si)2O5)2. Then preparing Al (Si) according to (Ni + Co + Al) in the precursor prepared in the step 12O5)2The molar ratio of Al in the alloy is 100:2, and the precursor and Al (Si) are weighed2O5)2And mixing them uniformly.
Step 3, lithiation:
according to step 2 [ obtained Al (Si)2O5)2(Ni + Co + Al) + coated Al (Si) in coated precursor2O5)2Al in (1)]The molar ratio of Li in the lithium salt is (100+2) { [ (100) +2 { (100)]X 1.05} and Al (Si) was weighed2O5)2The coated precursor and lithium hydroxide were mixed well.
Mixing Al (Si) with lithium salt2O5)2And calcining the coated precursor in an oxygen atmosphere at the sintering temperature of 750 ℃ for 17 hours. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 25:
step 1, precursor preparation, preparation steps as in example 24:
step 2, preparing a positive electrode material:
the precursor and lithium hydroxide were weighed and mixed uniformly, with the molar ratio of (Ni + Co + Al) in the precursor obtained in step 1 to Li in lithium hydroxide being 100: [ (100). times.1.05 ]. And calcining the precursor mixed with the lithium salt for 12 hours at 700 ℃ in an oxygen atmosphere. And after sintering, naturally cooling to room temperature to obtain the material, namely the lithium ion battery anode material.
Step 3, preparation of Al (Si)2O5)2：
Mixing Al in aluminum hydroxide and Si in aluminum dioxide at a molar ratio of 1:4, calcining at 500 deg.C in oxygen atmosphere for 4 hr to obtain Al (Si)2O5)2。
Step 4, coating the lithium ion battery anode material with LiAlSi4O10：
Al (Si) according to (Ni + Co + Al) in the positive electrode material prepared in the step 22O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is 100:1:1, and the mixture is uniformly mixed. The mixture was then calcined in an oxygen atmosphere at 500 ℃ for 2 h. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 26:
step 1, precursor preparation, preparation steps as in example 24:
step 2, preparing a positive electrode material:
the precursor and lithium hydroxide were weighed and mixed uniformly, with the molar ratio of (Ni + Co + Al) in the precursor obtained in step 1 to Li in lithium hydroxide being 100: [ (100). times.1.05 ]. And calcining the precursor mixed with the lithium salt for 12 hours at 700 ℃ in an oxygen atmosphere. And after sintering, naturally cooling to room temperature to obtain the material, namely the lithium ion battery anode material.
Step 3, preparation of Al (Si)2O5)2：
Mixing Al in aluminum hydroxide and Si in aluminum dioxide at a molar ratio of 1:4, calcining at 500 deg.C in oxygen atmosphere for 4 hr to obtain Al (Si)2O5)2。
Step 4, coating the lithium ion battery anode material with LiAlSi4O10：
Al (Si) according to (Ni + Co + Al) in the positive electrode material prepared in the step 22O5)2The molar ratio of Al in the lithium salt to Li in the doped MgO is 100:1:1:0.1, and uniformly mixing. The mixture was then calcined in an oxygen atmosphere at 700 ℃ for 2 h. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Example 27:
step 1, preparation of Al (Si)2O5)2：
According to the Al: the molar ratio of Si in the dioxide is 1:4, and the mixture is uniformly mixed and then calcined for 4 hours at 500 ℃ in an oxygen atmosphere to prepare Al (Si)2O5)2。
Step 4, coating the lithium ion battery anode material with LiAlSi4O10:
Al (Si) according to (Ni + Co + Mn) in the purchased positive electrode material2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is 100:1:1, and the mixture is uniformly mixed. The mixture was then calcined in an oxygen atmosphere at 500 ℃ for 2 h. After sintering, naturally cooling to room temperature to obtain the material LiAlSi4O10And (3) a coated lithium ion battery cathode material.
Claims (8)
1. LiAlSi4O10The coated lithium ion battery anode material is characterized in that an intermediate product Al (Si) is utilized2O5)2The method adopts a solid-phase synthesis method to carry out LiAlSi on the anode material of the lithium ion battery4O10Coating; the anode material of the lithium ion battery is a layered oxide, a lithium-rich manganese-based oxide, olivine lithium iron phosphate or spinel lithium manganate.
2. LiAlSi according to claim 14O10The preparation method of the coated lithium ion battery anode material is characterized by adopting an in-situ coating method and comprising the following steps of:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1 mol/L; dissolving a precipitant in water to ensure that the molar concentration of the precipitant is more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing a metal solution and a precipitant solution, stirring simultaneously, controlling the reaction temperature to be 30-85 ℃, controlling the reaction temperature to be 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 when regulating the pH value, wherein the protective gas is nitrogen, argon or carbon dioxide, centrifuging or suction-filtering and separating precipitates obtained by the reaction, and drying to obtain a precursor;
(2) coating the oxide by a hydrolysis method or a mixing method:
adopting a hydrolysis method:
weighing the precursor, tetraethoxysilane and aluminum isopropoxide according to the molar ratio of M in the precursor to Si in tetraethoxysilane to Al in aluminum isopropoxide of 100: alpha: beta, wherein the molar ratio is 0.4<α<10，0.1<β<2.5; dispersing/dissolving weighed precursors, ethyl orthosilicate and aluminum isopropoxide in a mixed solvent, wherein the molar ratio of alcohol to deionized water to acid or ammonia water is 100: epsilon: delta, 2<ε<2000，0.02<δ<0.5, carrying out suction filtration and drying to obtain powder; calcining the powder in air atmosphere, oxygen atmosphere or nitrogen atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to obtain an intermediate product Al (Si)2O5)2The coated precursor is in a nitrogen atmosphere when the precipitator in the step (1) is phosphate, and oxygen or air or nitrogen is used in the rest cases;
or a mixing method is adopted:
weighing silicon oxide, silicate or silicon-containing organic matter and aluminum oxide or salt according to the molar ratio of Si to Al in the silicon oxide, silicate or silicon-containing organic matter to be 4: 1; the weighed materials are evenly mixed and then calcined in the atmosphere of oxygen or air to prepare Al (Si)2O5)2The calcination temperature is 300-1100 ℃, and the calcination time is 0.5-18 hours; according to the precursor M, Al (Si) is prepared2O5)2The molar ratio of Al in the alloy is 100: beta, 0.1<β<2.5, weigh precursor and Al (Si)2O5)2And the weighed materials are mixed evenly,al (Si) is obtained2O5)2And a mixture of precursors;
(3) for Al (Si)2O5)2And carrying out lithiation treatment on the mixture of the precursor:
(3-1) to Al (Si)2O5)2And mixing the precursor mixture with lithium salt by any one of the following methods:
the first method comprises the following steps:
for the layered oxide and lithium iron phosphate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (100+ beta). times.1.05]Weighing Al (Si)2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 100 corresponds to M in the precursor, theoretical amount of lithium for the conversion of the precursor into a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, and 0.1<β<2.5；
The second method comprises the following steps:
for lithium-rich manganese-based oxides: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta) { [ (100+ pi) + beta]X 1.05} and Al (Si) was weighed2O5)2Coating the precursor and lithium salt, and uniformly mixing the weighed substances to obtain Al (Si) mixed with lithium salt2O5)2A mixture of precursors, where 100+ pi corresponds to the theoretical amount of lithium converted from the precursor to a lithium-rich manganese-based oxide, 100 corresponds to M in the precursor, the theoretical amount of lithium converted from the precursor to a conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) (Si2O5)2The Al content in the aluminum alloy is low,is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5 percent of lithium is needed to be added to supplement the amount of the volatilized lithium during high-temperature sintering, pi is more than or equal to 0 and less than or equal to 100, and 0.1<β<2.5；
The third method comprises the following steps:
for lithium manganate: according to said Al (Si)2O5)2M + coated Al (Si) in coated precursor2O5)2The molar ratio of Al in the lithium salt to Li in the lithium salt is (100+ beta): [ (50+ beta). times.1.05]Weighing Al (Si)2O5)2The coated precursor and lithium salt are evenly mixed to obtain Al (Si) mixed with lithium salt2O5)2Precursor mixture, where 50 is the theoretical amount of lithium converted from precursor to lithium manganate, 100 corresponds to M in precursor, the theoretical amount of lithium converted from precursor to conventional layered oxide and lithium iron phosphate, and β corresponds to Al (Si) and2O5)2al in (1) is Al (Si)2O5)2Conversion to LiAlSi4O101.05, 5% more lithium is needed to supplement the amount of volatilized lithium during high-temperature sintering, and 0.1<β<2.5；
(3-2) mixing the lithium salt with Al (Si)2O5)2Calcining the precursor mixture in air, oxygen or nitrogen atmosphere at 600-200 ℃ for 5-18 hours, and naturally cooling to room temperature to obtain LiAlSi4O10And (3) a coated lithium ion battery cathode material.
3. LiAlSi according to claim 14O10The preparation method of the coated lithium ion battery anode material is characterized in that an ex-situ coating method is adopted, and comprises the following steps:
(1) preparing a precursor:
(1-1) preparing a metal solution and a precipitant solution: dissolving soluble salt of metal M in water to make the total molar concentration of metal ions more than or equal to 1mol/L, and dissolving a precipitant in water to make the molar concentration of the precipitant more than or equal to 1 mol/L;
(1-2) precipitation reaction: mixing a metal solution and a precipitant solution, stirring, controlling the temperature to be 30-85 ℃ during 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 when regulating the pH value, wherein the protective gas is nitrogen, argon or carbon dioxide, centrifuging or suction-filtering and separating precipitates obtained by the reaction, and drying to obtain a precursor;
(2) preparing a positive electrode material:
(2-1) mixing the precursors with lithium salt by any one of the following methods:
the first method comprises the following steps:
for conventional layered oxides and lithium iron phosphate: weighing a precursor and a lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor of 100 [ (100). times.1.05 ], and uniformly mixing the weighed substances to obtain the precursor of the well-mixed lithium salt, wherein 100 corresponds to M in the precursor, namely the precursor is converted into the theoretical lithium amount of the traditional layered oxide and lithium iron phosphate, and 5% more lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering;
the second method comprises the following steps:
for lithium-rich manganese-based oxides: weighing the precursor and the lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor obtained in the step 1 being 100: [ (100+ pi) × 1.05], and uniformly mixing the precursor and the lithium salt to obtain a precursor mixed with the lithium salt, 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, 5% more 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 comprises the following steps:
for lithium manganate, weighing the precursor and lithium salt according to the molar ratio of M to Li in the lithium salt in the precursor obtained in the step 1 being 100 (50 x 1.05), and uniformly mixing the precursor and the lithium salt to obtain a precursor mixed with the lithium salt, wherein 50 is the theoretical lithium amount of the lithium manganate converted from the precursor, 100 corresponds to M in the precursor, and 5% more lithium is needed to supplement the volatilized lithium amount when 1.05 comes from high-temperature sintering;
(2-2) calcining the precursor mixed with the lithium salt in air, oxygen or nitrogen atmosphere at the sintering temperature of 600-1200 ℃ for 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 molar ratio of Al in aluminum oxide, aluminum hydroxide, aluminum acetate or aluminum nitrate to Si in silicon dioxide, silicate or silicon-containing organic matter being 1:4, uniformly mixing the weighed materials, calcining in an oxygen or air atmosphere at the temperature of 300-1100 ℃ for 0.5-18 hours to prepare Al (Si)2O5)2；
(4) Coating LiAlSi on the anode material of the lithium ion battery4O10：
According to M: Al (Si) in the cathode material (or purchased cathode material)2O5)2Weighing raw materials with the molar ratio of Al to Li in lithium salt of 100: beta, and uniformly mixing the weighed materials, wherein the molar ratio of Al to Li in lithium salt is 0.1<β<2.5; calcining the mixture in air, oxygen or nitrogen atmosphere for 0.5-6 hours at 300-700 ℃, and naturally cooling to room temperature to obtain the LiAlSi4O10And (3) a coated lithium ion battery cathode material.
4. The method for preparing the positive electrode material of the lithium ion battery according to claim 2 or 3, wherein the metal M 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 and B.
5. The method for producing a positive electrode material for a lithium ion battery according to claim 2 or 3, wherein the soluble salt of the metal M is a sulfate, a nitrate, an acetate, a sulfite, or a nitrite.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 2 or 3, wherein the precipitant is one or more of oxalate, carbonate, hydroxide and phosphate.
7. The preparation method of the lithium ion battery cathode material according to claim 2 or 3, 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.
8. The method for preparing the positive electrode material of the lithium ion battery according to claim 2 or 3, wherein the lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium nitrate.
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