CN115084515B - Inorganic oligomer lithium-containing compound metal oxide material, preparation method thereof and application thereof in lithium ion battery anode material - Google Patents
Inorganic oligomer lithium-containing compound metal oxide material, preparation method thereof and application thereof in lithium ion battery anode material Download PDFInfo
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- CN115084515B CN115084515B CN202110263774.3A CN202110263774A CN115084515B CN 115084515 B CN115084515 B CN 115084515B CN 202110263774 A CN202110263774 A CN 202110263774A CN 115084515 B CN115084515 B CN 115084515B
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- lithium
- metal oxide
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- inorganic oligomer
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- 239000000463 material Substances 0.000 title claims abstract description 159
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 120
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 100
- -1 compound metal oxide Chemical class 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 title description 10
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 82
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 138
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 126
- 239000002131 composite material Substances 0.000 claims description 92
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 64
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 150000004645 aluminates Chemical class 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- 239000007773 negative electrode material 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
- 239000010452 phosphate Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 43
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 124
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 62
- 238000000034 method Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 23
- 238000004108 freeze drying Methods 0.000 description 19
- 230000014759 maintenance of location Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- 239000000084 colloidal system Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 10
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229940032296 ferric chloride Drugs 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 241001559547 Hippocampus comes Species 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910016049 LixMOy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an inorganic oligomer lithium-containing compound metal oxide material, a preparation method thereof and application thereof in a lithium ion battery cathode material. The outer layer of the inorganic oligomer lithium-containing compound metal oxide material is an inorganic oligomer lithium-containing compound with an amorphous structure, and the inner layer is a metal oxide; the mass ratio of the metal oxide to the inorganic oligomer lithium content is 1: (0.01 to 0.5), preferably 1: (0.01-0.1); the structural general formula of the metal oxide is N u O v Wherein N is selected from at least one of iron element, cobalt element, manganese element, nickel element, titanium element and niobium element, and u is more than or equal to 1 and less than or equal to 3, v is more than or equal to 1 and less than or equal to 4; the structural general formula of the inorganic oligomer lithium-containing material is Li x MO y Wherein M is at least one selected from phosphorus element, silicon element, boron element and aluminum element, and is less than or equal to 1 percentx≤3，1≤y≤5。
Description
Technical Field
The invention relates to an inorganic oligomer lithium-containing compound metal oxide material, a preparation method thereof and application thereof in a lithium ion battery negative electrode material, in particular to a solution containing a lithium compound prepared by an oligomer method and application thereof as an additive compound metal oxide material and application thereof in a lithium ion battery negative electrode material.
Background
Since 1991, lithium Ion Batteries (LIBs) using lithium cobaltate as a positive electrode and graphite as a negative electrode were developed by sony corporation in japan, they have been rapidly and widely used by virtue of their high capacity, high operating voltage, long cycle life, low self-discharge rate, and the like. Electric vehicles are an important part of many applications for lithium ion batteries, and higher energy and power densities are urgently needed to meet the demand. The energy density of LIBs is mainly dependent on the voltage difference between the positive and negative electrodes and the specific capacity of the electrode material (mAh g in a suitable potential window -1 Or mAh L -1 ) The power density is mainly dependent on the specific capacities of the positive and negative electrodes at different current densities. Therefore, the development of high-voltage positive electrode and high-capacity negative electrode materials is largely explored as a main development direction of lithium ion batteries. Graphite is a negative electrode material that has achieved wide commercial use, but its lower energy density (372 mAh g -1 ) Limiting its further application. Metal oxide (N) x O y ) Because of the advantages of higher capacity, low cost, environmental friendliness and the like, the graphite composite material is widely paid attention to and has the potential of replacing graphite to become a new-generation negative electrode material. Conventional metal oxide materials have problems when applied as cathodes, which greatly limit their further application. (1) In the first lithiation/delithiation process, irreversible side reactions on the material surface and formation of Solid Electrolyte Interface (SEI) films result in low Initial Coulombic Efficiency (ICE). (2) The volume expansion effect during continuous charge and discharge causes particle pulverization, thereby leading to formation of an unstable SEI layer and aggregation of metal simple substance particles, and finally causing capacity attenuation and cycle life reduction of the battery. (3) The conductivity and lithium ion transport efficiency of the metal oxide material are poor.
Scientists have made many efforts to solve the problems of metal oxide anode materials from the point of material design, with significant results. Such as compounding metal oxides in a material having low expansionVarious carbon materials with high rate and high conductivity to improve the cycle stability of metal oxide negative electrode, huang et al (Electrochimica Acta 260 (2018) 965e 973) crosslinked nanocarbon modified Fe 2 O 3 The composite material has excellent capacity and stable cycle performance, but a large amount of metal oxide cathodes composited by using non-active substances carbon often have lower initial coulombic efficiency and volumetric specific energy density. In addition, researches show that the coarsening of crystal grains caused by cyclic charge and discharge is an important reason (Energy Environmental Science (2017) 2017) for causing slow dynamics of the metal oxide anode material, more interfaces and crystal boundaries can be exposed through material nanocrystallization, the coarsening of the crystal grains is restrained, the lithium ion transmission distance is shortened, and the performance of the electrode material is further improved. Synthesis of nanoporous Fe using Fe-MOF templates as in Fan et al (2D Materials 6 (2019) 045022) 2 O 3 The hybrid network obtains excellent high-rate capacity, but the nanocrystallization of the material inevitably causes the aggravation of side reactions and influences the long-cycle stability. The above methods have largely proven to improve the performance of metal oxide materials, but these optimization methods have drawbacks and are relatively difficult to control, time consuming, labor consuming, costly under industrial scale manufacturing conditions, greatly limiting their potential for application.
Disclosure of Invention
In order to solve the problems, the invention provides an inorganic oligomer lithium-containing compound metal oxide material, a preparation method thereof and application thereof in a lithium ion battery anode material.
In a first aspect, the present invention provides an inorganic oligomer lithium-containing composite metal oxide material, wherein an outer layer of the inorganic oligomer lithium-containing composite metal oxide material is an inorganic oligomer lithium-containing material (or referred to as an inorganic oligomer lithium-containing compound) with an amorphous structure, and an inner layer is a metal oxide; the mass ratio of the metal oxide to the inorganic oligomer lithium content is 1: (0.01 to 0.5), preferably 1: (0.01-0.1); the structural general formula of the metal oxide is N u O v Wherein N is selected from at least one of iron element, cobalt element, manganese element, nickel element, titanium element and niobium element, and u is more than or equal to 1 and less than or equal to 3, v is more than or equal to 1 and less than or equal to 4; the inorganic oligomerThe structural general formula of the lithium-containing material is Li x MO y Wherein M is at least one of phosphorus element, silicon element, boron element and aluminum element, x is more than or equal to 1 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 5.
In the invention, the inorganic oligomer lithium-containing compound metal oxide material has rich pore canal structure (the porosity is 13.5%), uniform and controllable amorphous lithium-containing compound modified layer and rapid lithium ion transport property. Good lithium storage performance of the composite metal oxide material can be realized through the amorphous structure and uniform coating of the lithium-containing material.
Preferably, the size of the inorganic oligomer lithium-containing compound metal oxide material is 0.1-20 mu m, and the specific surface area is more than 210m 2 /g。
Preferably, the inorganic oligomer lithium-containing material is lithium phosphate and the metal oxide is ferric oxide. The ferric oxide material has low price, relatively simple preparation and higher theoretical capacity (about 1000mAh g) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium phosphate is a typical fast lithium ion conductor, and when used as a coating layer, can promote the rapid transmission of lithium ions at a surface interface, and can also protect ferric oxide from electrolyte attack.
Preferably, the size of the metal oxide material is 100 nm-20 mu m; the metal oxide material is a secondary particle (morphology is shown in fig. 11) formed by stacking primary particles having a size of 10nm to 1 μm, preferably, a primary particle size of 10nm to 500nm. When the lithium ion battery anode material is used as a lithium ion battery anode material, the particle size has a great influence on the performance, and when the particle size is large, the diffusion distance from the surface to the bulk phase of lithium ions is prolonged, the transmission is slowed down, and the performance is represented by the deterioration of high-rate (high-current charge and discharge) performance; when the particles are too small, the lithium ion transport distance is shortened, but the area of direct contact with the electrolyte is increased, the side reaction with the electrolyte is aggravated, and the cycle retention rate is easily reduced. The electrochemical performance can be optimized by selecting a suitable particle size.
Preferably, the inorganic oligomer lithium-containing material is Li formed by repeated covalent bond connection of monomers + And MO (metal oxide semiconductor) y -z Short multimers of (2), single units thereofThe number of the bodies is less than or equal to 20.
The principle of the formation of the inorganic oligomer lithium-containing material is that the formed monomer Li is formed through the end capping of triethylamine x MO y No rapid polymerization to form precipitate occurs, the specific principle is as follows: the method is characterized in that the hydrogen atoms in triethylamine molecules and oxygen atoms in oligomer monomers are combined preferentially through hydrogen bonds, so that polycondensation reaction between the monomers is prevented (taking lithium phosphate oligomer as an example, the hydrogen atoms in triethylamine and the oxygen atoms in lithium phosphate monomers are combined preferentially through hydrogen bonds, so that lithium phosphate monomers cannot polymerize, lithium phosphate precipitation is avoided due to the fact that solution is uniform and stable, the quantity of the monomers of a product (LixMOy) N is small by controlling the proportion of cations to triethylamine, the triethylamine content in unit volume of the solution is increased along with the increase of the molar ratio of cations to triethylamine, N.H-O hydrogen bonds (N.H.comes from triethylamine, O is from lithium phosphate/lithium borate and the like) are more easily formed, the monomer connection quantity of the oligomer lithium-containing substances is smaller, and generally when Li is less than 1:8, the quantity of the product monomers formed is less than or equal to 20 when Li is less than 1:8.
Preferably, the preparation method of the inorganic oligomer lithium-containing material solution comprises the following steps: dispersing soluble lithium salt in ethanol, adding triethylamine, stirring thoroughly, adding at least one of soluble phosphorus, boron, silicon and aluminate dropwise, and stirring uniformly to obtain inorganic oligomer lithium-containing solution.
In the invention, a method for preparing a stable inorganic oligomer lithium-containing compound is disclosed by utilizing a formation mechanism of an oligomer in a high polymer material. The ethanol solvent with lower dielectric constant can promote the triethylamine to form hydrogen bonds with the monomers. By using triethylamine as a blocking agent, a lithium compound which can be dissolved in ethanol is used as a lithium source, at least one of phosphorus, boron, silicon and aluminate is used as an anion source, and a method of dropwise adding anion and cation solutions is adopted, and the blocking effect of the triethylamine is utilized to prevent precipitation reaction of anions and cations so as to form a uniform non-precipitated lithium compound-containing oligomer solution Li x MO y The chemical composition and form of the product dependThe preparation method avoids precipitation and particle growth of lithium-containing compounds in the proportion of triethylamine to cations, the types of anions and specific reaction conditions.
Preferably, the molar ratio of the soluble lithium salt to the triethylamine is 1: (6 to 100), preferably 1: (8-100). The more triethylamine content, the more stable the solution of the obtained inorganic oligomer lithium-containing substance, the less prone to spontaneous precipitation.
Preferably, the mole ratio of the soluble lithium salt to the soluble phosphate, boron, silicon and aluminate salt is (1-3): (1-5), preferably (2-3): 1.
Preferably, the lithium salt is at least one of lithium chloride, lithium nitrate, lithium sulfate and lithium hydroxide, and preferably lithium nitrate; the soluble phosphorus, boron, silicon and aluminate is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, silicic acid, boric acid, metaboric acid, aluminate and the like, and preferably phosphoric acid. Phosphoric acid is selected to produce lithium phosphate oligomers, which can remove the interference of cations in phosphate-containing drugs.
In a second aspect, the present invention provides a method for preparing the above inorganic oligomer lithium-containing composite metal oxide material, comprising: the metal oxide N u O v And adding solid powder into the inorganic lithium-containing oligomer solution, rapidly stirring until the liquid is completely volatilized, and drying to obtain the inorganic lithium-containing oligomer composite metal oxide material.
In the invention, lithium-containing substances synthesized by an inorganic oligomer method are compounded on metal oxides to prepare the metal oxide anode material with excellent lithium storage performance. Specifically, triethylamine is used as a blocking agent to form a uniform non-precipitation solution of the lithium-containing compound, then metal oxide powder is added into the solution, and the final product is obtained after stirring, evaporating and drying. It should be noted that when preparing the inorganic oligomeric lithium-containing compound, triethylamine is added first, followed by a solution of soluble compound containing at least one of phosphorus, boron, silicon, aluminate. Taking ferric chloride hexahydrate, lithium nitrate and phosphoric acid as reagents for example, firstly preparing the ferric chloride hexahydrate into a uniform solution with a certain concentration, then dropwise adding ammonia water, fully stirring, and carrying out solid-liquid separation and drying to obtain ferric oxide solid; dissolving lithium nitrate in ethanol, adding a proper amount of triethylamine, fully stirring, adding phosphoric acid, and uniformly stirring to form a semitransparent inorganic oligomer lithium phosphate solution; and adding the prepared ferric oxide solid powder into an inorganic oligomer lithium phosphate solution, stirring at a certain temperature, evaporating to dryness, and drying to obtain the inorganic oligomer lithium phosphate composite ferric oxide material.
Preferably, the metal oxide N u O v The solid powder is prepared by a high-temperature solid phase method, a sol-gel method, a hydrothermal synthesis method or a precipitation method.
Preferably, the metal oxide N u O v The mass ratio of the solid powder to the inorganic lithium-containing oligomer solution is 1: (0.01-0.5).
Preferably, the temperature of the stirring is 30 to 95 ℃, preferably 60 to 80 ℃.
Preferably, the drying method is vacuum drying method, freeze drying method or supercritical drying method.
In a third aspect, the invention provides the use of the inorganic oligomer lithium-containing composite metal oxide material described above on a lithium ion battery cathode. The inorganic oligomer lithium-containing compound metal oxide material has rich pore canal structure and controllable modification layer thickness, and shows high capacity, high multiplying power and high stability when used as a lithium ion battery anode material.
The beneficial effects are that:
1. the inorganic oligomer lithium-containing compound is mixed with metal oxide after modification treatment, and the surface of the metal oxide is uniformly coated with a layer of amorphous lithium-containing compound to obtain the inorganic oligomer lithium-containing compound metal oxide material. The porous structure formed by coating the composite material can effectively improve the specific surface area of the composite material, so as to further relieve the volume expansion effect in the electrochemical process, in addition, the pore channel structure can promote the infiltration of electrolyte, shorten the lithium ion transmission distance, improve the rate capability of the material, effectively protect the metal oxide by the lithium-containing coating layer, and improve the circulation stability of the material.
2. The invention can further improve the lithium storage capacity of the composite material and show good rate capability and cycle stability by further optimizing the composition and coating thickness of the inorganic oligomer lithium-containing material.
3. The invention has simple preparation process, low cost, strong controllability, good repeatability and excellent lithium storage performance.
Drawings
FIG. 1 shows an X-ray diffraction pattern (b) of iron oxide (a) and oligomeric lithium phosphate composite iron oxide prepared in example 1 of the present invention.
Fig. 2 shows a Scanning Electron Microscope (SEM) (a) and a Transmission Electron Microscope (TEM) (b) of the oligomeric lithium phosphate composite iron oxide prepared in example 1 of the present invention.
Fig. 3 shows a nitrogen adsorption and desorption curve of the oligomeric lithium phosphate composite iron oxide prepared in example 1 of the present invention.
Fig. 4 shows a first charge-discharge curve of the oligomeric lithium phosphate composite iron oxide material prepared in example 1 of the present invention as a negative electrode of a lithium ion battery.
Fig. 5 shows a comparison graph of the rate performance of the oligomeric lithium phosphate composite iron oxide prepared in example 1 of the present invention and the nano iron oxide material prepared in comparative example 1 as a negative electrode of a lithium ion battery.
Fig. 6 is a graph showing comparison of cycle charge and discharge performance of the oligomeric lithium phosphate composite iron oxide prepared in example 1 of the present invention and the nano iron oxide material prepared in comparative example 1 as a negative electrode of a lithium ion battery.
Fig. 7 shows XRD patterns of the oligomeric lithium phosphate composite iron oxide prepared in example 2 of the present invention.
Fig. 8 shows SEM (a) and TEM (b) of the oligomeric lithium phosphate composite iron oxide prepared in example 2 of the present invention.
Fig. 9 shows a nitrogen adsorption and desorption curve of the oligomeric lithium phosphate composite iron oxide prepared in example 2 of the present invention.
Fig. 10 shows a first charge-discharge graph of the oligomeric lithium phosphate composite iron oxide material prepared in example 2 of the present invention as a negative electrode of a lithium ion battery.
Fig. 11 shows an SEM image of the metal oxide material prepared in example 3 of the present invention.
Detailed Description
The following describes in further detail the specific embodiments of the present invention with reference to the drawings and examples. It is to be understood that the following drawings and examples are illustrative of the present invention and are not to be construed as limiting the invention.
Aiming at the current situations of poor lithium storage performance and complex modification process of the metal oxide material, the invention provides a metal oxide composite material with high capacity, high ploidy and cycle stability and a preparation method thereof by utilizing the advantage that an inorganic oligomer lithium-containing compound (in a uniform and stable solution state) can be effectively coated on the surface of the metal oxide material.
In the present disclosure, an inorganic oligomer lithium-containing composite metal oxide material having a porous structure may be used as a lithium ion battery anode material, the particles of which are nano-structured, the outer layer of the composite material being a lithium-containing compound, and the inner layer being a metal oxide, such as iron oxide. The mass ratio of the metal oxide to the lithium-containing compound may be 1: (0.01 to 0.5), preferably 1: (0.01-0.1). In range 1: when (0.01 to 0.5), the cyclic stability (capacity retention) of the material is not substantially changed, and the capacity is slightly reduced. Wherein the structural general formula of the metal oxide material is N u O v Wherein N is selected from one or more of iron element, cobalt element, manganese element, nickel element, titanium element and niobium element, and u is 1-3, v is 1-5, preferably iron element, namely Fe u O v . The inorganic oligomer lithium-containing compound is a novel method for preparing lithium-containing compound, the lithium-containing compound has an amorphous structure and can exist in ethanol solution uniformly and stably in a solution form, and the structural general formula is Li x MO y Wherein M is at least one selected from phosphorus element, silicon element, boron element and aluminum element, and x is more than or equal to 1 and less than or equal to 3, y is more than or equal to 1 and less than or equal to 5, and is preferably Li 3 PO 4 。
In the present invention, a method for preparing a stable inorganic oligomer lithium-containing compound is disclosed by utilizing the formation mechanism of an oligomer in a high molecular material, wherein the oligomer is oneThe short polymer formed by repeated covalent bond connection of a small number of monomers is Li + And MO (metal oxide semiconductor) -z y The number of monomers is less than or equal to 20. The method comprises the steps of using triethylamine as a blocking agent, using a lithium compound which can be dissolved in ethanol as a lithium source and at least one of phosphorus, boron, silicon and aluminate as an anion source, adopting a method of respectively adding anion solution and cation solution dropwise, and preventing precipitation reaction of anions and cations by using the blocking effect of the triethylamine to form a uniform non-precipitated lithium compound oligomer solution Li x MO y . The reason for the drop-wise addition is to prevent the formed oligomer from precipitating, because too fast addition of soluble phosphorus, boron, silicon and aluminate salts can cause a higher concentration of local anions (soluble phosphorus, boron, silicon and aluminate) in the original system (lithium/triethylamine/ethanol mixed solution), so that precipitation of the lithium-containing compound is directly generated, and the advantage that the oligomer lithium-containing compound is a uniformly dispersed solution is lost. The experiment is completed by adopting a mode of stirring the solution of the original system (lithium/triethylamine/ethanol mixed solution) and dropwise adding the anion solution by using a rubber head dropper. The chemical composition and form of the product will depend on the ratio of triethylamine to cation, the type of anion and the specific reaction conditions. The preparation method avoids precipitation and particle growth of the lithium-containing compound, and can effectively and uniformly compound on the surface of the metal oxide material when the lithium-containing compound is used as an additive, thereby having unique advantages.
In the present invention, the size of the metal oxide material may be 100nm to 20. Mu.m, preferably 100nm to 10. Mu.m. The metal oxide material is a secondary particle formed by stacking primary particles, and the primary particle size may be 10nm to 1 μm, and preferably, the primary particle size may be 10nm to 500nm. The lithium-containing compound ethanol solution prepared by the oligomer method is used as an additive to compound the metal oxide material, the lithium-containing compound can be uniformly compounded on the surface of the material in the form of an amorphous nano material, and the size of the compound metal oxide material can be 0.1-20 mu m. The composite material has rich specific surface area, and the specific surface area is more than 210m 2 /g。
The following exemplifies a method for preparing the inorganic oligomer lithium-containing composite metal oxide material provided by the present invention.
Preparation of metal oxide N u O v . Wherein N is selected from one or more of iron element, cobalt element, manganese element, nickel element, titanium element and niobium element, and u is more than or equal to 1 and less than or equal to 3, v is more than or equal to 1 and less than or equal to 5, preferably iron element, namely Fe u O v The preparation method comprises, but is not limited to, a high-temperature solid phase method, a sol-gel method, a hydrothermal synthesis method, a precipitation method and the like.
An inorganic oligomer lithium-containing compound solution is prepared by adopting an oligomer method. Dispersing soluble salt of lithium and triethylamine in ethanol, stirring until the solution is dissolved to obtain a clear solution, continuously adding an ethanol solution containing at least one of soluble phosphorus, boron, silicon and aluminate, and continuously stirring to obtain a uniform inorganic oligomer lithium-containing compound solution. As one example, the soluble salts of lithium can be dissolved in ethanol, including but not limited to lithium chloride, lithium nitrate, lithium sulfate, lithium hydroxide. The soluble phosphorus, boron, silicon, aluminate containing can be dissolved in ethanol including, but not limited to, at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, silicic acid, boric acid, metaboric acid, aluminate, and the like. The atomic mole ratio of the soluble salt of lithium to triethylamine is 1 (6-100), preferably 1 (8-100), and the more the triethylamine content is, the more stable the obtained lithium-containing compound oligomer solution is, the less precipitate of the lithium-containing compound is generated. The mole ratio of the soluble lithium salt to the soluble phosphate, boron, silicon and aluminate is (1-3): (1-5), preferably (2-3): 1.
The inorganic oligomer lithium-containing compound solution is mixed with the metal oxide. Dispersing metal oxide powder in an inorganic oligomer lithium-containing compound solution, heating, stirring and volatilizing until the liquid is completely volatilized, and drying to obtain the inorganic oligomer lithium-containing compound metal oxide material. As one example, the mass ratio of metal oxide to lithium-containing compound may be 1: (0.01 to 0.5), preferably 1:0.5. the heating and stirring temperature is 30-95 ℃, preferably 60-80 ℃. The amount of triethylamine added in different proportions will result in different mass of oligomer lithium-containing compound per unit volume, and in practical experiments the amount of product oligomer lithium-containing compound is determined according to the amount of added material (fixed amount of triethylamine and ethanol, mass of product oligomer lithium-containing compound is determined according to the amount of added lithium salt and soluble phosphorus, boron, silicon, aluminate anions), and when metal oxides are mixed, metal oxides are as follows: the lithium-containing compound is added in a mass ratio.
As an example of a detailed preparation of the oligomeric lithium phosphate composite iron oxide material, the preparation procedure is as follows:
(1) Dispersing soluble ferric salt in water, adding ammonia water solution, stirring until uniform and stable sol is formed, separating solid from liquid, and drying to obtain ferric oxide powder. As an example, ferric chloride hexahydrate is dissolved in water to form a uniform solution, a proper amount of ammonia water is added dropwise, the mixture is stirred and aged for a period of time, and the mixture is subjected to centrifugal solid-liquid separation and dried to obtain ferric oxide (Fe) u O v U is more than or equal to 1 and less than or equal to 3, v is more than or equal to 1 and less than or equal to 5).
(2) Dispersing soluble lithium salt in ethanol, adding triethylamine, fully stirring, adding an ethanol solution of soluble phosphate, and stirring uniformly to obtain an oligomer lithium phosphate solution. As an example, lithium nitrate is dissolved in ethanol, triethylamine can be added according to the mol ratio of more than or equal to 1:8, then phosphoric acid solution is added, and the solution is fully stirred to obtain stable lithium phosphate oligomer solution.
(3) Mixing the obtained ferric oxide powder with a certain amount of oligomer lithium phosphate solution, stirring and evaporating to dryness at a certain temperature, and drying to obtain the oligomer lithium phosphate composite ferric oxide material. As one example, an appropriate amount of iron oxide powder is mixed with an oligomeric lithium phosphate solution. The mass ratio of the addition amount of the ferric oxide powder to the oligomeric lithium phosphate solution can be 1: (0.01-0.5). The inorganic oligomer lithium phosphate composite ferric oxide material can be obtained after stirring and volatilizing at 60-80 ℃ until only solid is left and drying.
The invention prepares lithium-containing compound solution which is uniform and does not precipitate through an inorganic oligomer method, and mixes and dries the oligomer lithium-containing compound solution and metal oxide powder to obtain the inorganic oligomer lithium-containing compound metal oxide material. The material has rich pore canal structure and uniform content The lithium coating layer, when used as a negative electrode of a lithium ion battery, exhibits good electrochemical properties. The main advantages are as follows: first, inorganic oligomer process prepares lithium-containing compound, and due to the presence of triethylamine as end capping agent, the precipitation reaction is prevented to form Li + And MO (metal oxide semiconductor) -z y The number of monomers of the short polymer is less than or equal to 20, and the short polymer can exist stably in a solution form. Secondly, when the lithium-containing compound solution is formed by an oligomer method and the metal oxide is compounded, the lithium-containing compound can be coated on the surface of the metal oxide material more uniformly in an amorphous material state, more pore channel structures are manufactured, the specific surface area of the material is improved, and when the lithium-containing compound solution is used as an electrode material, the volume expansion and the coarsening of crystal grains can be effectively relieved, and the circulation stability is improved. Thirdly, the uniform lithium-containing compound coating layer can effectively improve lithium ion transmission, improve the multiplying power performance of the battery, and also can effectively protect the active substance metal oxide from corrosion of side reaction, thereby improving the lithium storage stability. Fourth, the inorganic oligomer lithium-containing material modified composite metal oxide material obtained by the invention has larger specific surface area, excellent lithium storage capacity and cycle stability. In general, the inorganic oligomer lithium-containing composite metal oxide material prepared by the method has a simpler preparation process and excellent lithium storage performance.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
Dispersing 2.70g of ferric chloride hexahydrate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) for continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
2.07g of lithium nitrate was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 60 minutes to form a homogeneous solution, followed by 0.98g of phosphoric acid (98 wt% by mass) was added, and stirred sufficiently for 30 minutes to form a homogeneous oligomer solution.
Taking 4.31ml of oligomer solution (wherein the oligomer lithium phosphate is 0.02 g) and 0.40g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the oligomer lithium phosphate modified ferric oxide material.
The iron oxide powder prepared in example 1 was shown in fig. 1 (a) using an X-ray diffractometer, and it is apparent that the iron oxide prepared by the ammonia-assisted precipitation method was an amorphous material, and the powder diffraction pattern of the oligomeric lithium phosphate composite iron oxide material prepared in example 1 was shown in fig. 1 (b), and it was apparent that the diffraction pattern of the iron oxide material was not substantially changed, but some more bulges were present because the composite lithium phosphate was present in an amorphous form.
Fig. 2 (a) shows a topography of the composite iron oxide material prepared in example 1, as measured using a scanning electron microscope. Fig. 2 (b) shows a microstructure of the iron oxide material tested using a transmission electron microscope. As shown in a of fig. 2, it is obvious that the prepared composite ferric oxide has rich pore canal structure and a modified layer on the surface. As can be seen from b in fig. 2, the iron oxide nanocrystals are uniformly distributed in the amorphous lithium phosphate.
FIG. 3 is a nitrogen isothermal adsorption/desorption line obtained by testing an oligomeric lithium phosphate composite ferric oxide material prepared in example 1 using a specific surface area tester, and a specific surface area of 212.76m was calculated by using a BET (Brunauer Emmet Teller) formula 2 And/g. Calculating the specific surface area by using BET is a common method for testing mesoporous micropores, specifically, a section between p/p0=0.05-0.35 in isothermal adsorption and desorption of nitrogen is processed by using a BET formula to obtain single-layer adsorption amount data Vm, and then the specific surface area is calculated according to the single-layer adsorption amount data Vm.
The electrochemical performance of the prepared oligomer lithium phosphate composite ferric oxide material passes the button cell test. Specifically: according to the active substances: PVDF: acetylene black=8:1:1 (mass ratio), the mixture was weighed and smeared, then dried in vacuo at 90 ℃, cut into pole pieces with a diameter of about 12mm, and the assembled battery was left to stand for 12 hours and then subjected to various electrochemical performance tests. The test voltage is between 0.01 and 3V, and the first discharge capacity of the oligomeric lithium phosphate composite ferric oxide material prepared in the example 1 can reach 1113mAh g -1 Compared with the nano ferric oxide material of comparative example 1 (fig. 4), the charge and discharge capacity of the oligomeric lithium phosphate composite ferric oxide material prepared in example 1 under different multiplying powers is also obviously improved (fig. 5), and the capacity retention rate of 1000 circles of 1C current is more than 90% (fig. 6).
Example 2
Dispersing 1.62g of ferric chloride in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
1.27g of lithium chloride was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 30 minutes to form a uniform solution, followed by 0.98g of phosphoric acid (98% by mass) was added, and stirred sufficiently for 60 minutes to form a uniform sol solution.
Taking 4.31ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the oligomeric lithium phosphate composite ferric oxide material.
Fig. 7 is a result of testing the composite iron oxide material powder prepared in example 2 using an X-ray diffractometer. It can be obviously seen that the prepared composite ferric oxide material is an amorphous material.
Fig. 8 (a) shows a morphology diagram of the composite iron oxide material prepared in example 2, which is tested by using a scanning electron microscope, and as shown in the figure, the composite iron oxide has a rich pore structure, and the surface coating layer is lithium phosphate. Fig. 8 (b) shows the microstructure of the composite iron oxide material prepared in example 2, which was tested using a transmission electron microscope, and it can be seen that the prepared iron oxide had nanocrystals distributed in amorphous lithium phosphate. When used as a lithium ion electrode material, the amorphous lithium phosphate can effectively protect ferric oxide from corrosion caused by side reactions and promote ion transmission.
FIG. 9 is a nitrogen isothermal adsorption/desorption line of a lithium phosphate modified iron oxide material prepared in example 2, which was measured using a specific surface area tester, and the BET specific surface area of the lithium phosphate modified iron oxide material was 215.80m 2 And/g. The electrochemical performance of the prepared oligomer lithium phosphate composite ferric oxide material passes the button cell test. Specifically: according to the active substances: PVDF: acetylene black=8:1:1 (mass ratio), the mixture was weighed and smeared, then dried in vacuo at 90 ℃, cut into pole pieces with a diameter of about 12mm, and the assembled battery was left to stand for 12 hours and then subjected to various electrochemical performance tests. The voltage is between 0.01 and 3V, and the first discharge capacity reaches 1148mAh g -1 (FIG. 10), the capacity retention rate was greater than 90% for 1000 cycles of 1C current.
Example 3
Dispersing 4g of ferric sulfate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifuge (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder. 1.27g of lithium chloride was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 30 minutes to form a uniform solution, followed by 0.98g of phosphoric acid (98% by mass) was added, and stirred sufficiently for 60 minutes to form a uniform sol solution. Taking 4.31ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the composite ferric oxide material.
The electrochemical performance of the prepared composite ferric oxide material passes the button cell test. Specifically: according to the active substances: PVDF: acetylene black=8:1:1 (mass ratio), the mixture is weighed and smeared, then vacuum dried at 90 ℃,cutting into pole pieces with the diameter of about 12mm, standing the assembled battery for 12 hours, and then carrying out various electrochemical performance tests. The voltage is between 0.01 and 3V, and the first discharge capacity reaches 1110mAh g -1 The capacity retention rate of 1000 cycles under 1C current is more than 90 percent.
Example 4
Dispersing 4g of ferric sulfate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifuge (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
Dispersing 1.27g lithium chloride in 200ml ethanol, adding 50ml triethylamine, stirring for 30min to obtain a uniform solution, and adding 100ml diammonium hydrogen phosphate (dissolved in water to form 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
Taking 6.03ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the composite ferric oxide material.
The electrochemical performance of the prepared composite ferric oxide material passes the button cell test. Specifically: according to the active substances: PVDF: acetylene black=8:1:1 (mass ratio), the mixture was weighed and smeared, then dried in vacuo at 90 ℃, cut into pole pieces with a diameter of about 12mm, and the assembled battery was left to stand for 12 hours and then subjected to various electrochemical performance tests. The voltage is between 0.01 and 3V, and the first discharge capacity reaches 1045mAh g -1 The capacity retention rate at 1C current for 500 cycles is greater than 90%.
Example 5
Dispersing 4g of ferric sulfate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifuge (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
Taking 1.27g of lithium chloride was dispersed in 200ml of ethanol, 50ml of triethylamine was added thereto, and stirred for 30 minutes to form a homogeneous solution, followed by addition of 100ml of boric acid (dissolved in ethanol to form 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
Taking 6.03ml of sol solution (wherein the oligomer lithium borate is 0.02 g) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the composite ferric oxide material. The electrochemical performance of the prepared composite ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite ferric oxide material is more than 90 percent after 500 circles of circulation under 1C current.
Example 6
Dispersing 4g of ferric sulfate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifuge (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
Dispersing 1.27g lithium chloride in 200ml ethanol, adding 50ml triethylamine, stirring for 30min to obtain uniform solution, and adding 100ml silicic acid (dissolved in ethanol to obtain 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
Taking 5.55ml of sol solution (wherein the oligomer lithium silicate is 0.02 g) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the composite ferric oxide material. The electrochemical performance of the prepared composite ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite ferric oxide material is more than 90 percent after 500 circles of circulation under 1C current.
Example 7
Dispersing 1.62g of ferric chloride in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
Dispersing 1.27g lithium chloride in 200ml ethanol, adding 50ml triethylamine, stirring for 30min to obtain uniform solution, and adding 100ml metaboric acid (dissolved in ethanol to obtain 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
10ml of sol solution (wherein the oligomer lithium metaborate is 0.02 g) and 0.4g of ferric oxide powder are taken, stirred at 50 ℃ until the liquid is completely volatilized, and the obtained powder is dried in an oven for 24 hours to obtain the composite ferric oxide material. The electrochemical performance of the prepared composite ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite ferric oxide material is more than 90 percent after 500 circles of circulation under 1C current.
Example 8
Dispersing 1.62g of ferric chloride in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), and performing freeze drying to obtain ferric oxide solid powder.
Dispersing 1.27g lithium chloride in 200ml ethanol, adding 50ml triethylamine, stirring for 30min to obtain a uniform solution, and adding 100ml aluminate (dissolved in water to obtain 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
Taking 3.80ml of sol solution (wherein the oligomer lithium aluminate is 0.01 g) and 0.4g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the composite ferric oxide material. The electrochemical performance of the prepared composite ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite ferric oxide material is more than 90 percent after 500 circles of circulation under 1C current.
Example 9
Dispersing 1.30g of cobalt chloride in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) and continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), performing freeze drying to obtain solid powder, and annealing at 400 ℃ for 2h in a tubular furnace to obtain the cobaltosic oxide.
Dispersing 1.27g lithium chloride in 200ml ethanol, adding 50ml triethylamine, stirring for 30min to obtain a uniform solution, and adding 100ml diammonium hydrogen phosphate (dissolved in water to form 0.1mol L) -1 Is stirred sufficiently for 60min to form a uniform sol solution.
Taking 6.03ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of cobaltosic oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the composite cobaltosic oxide material. The electrochemical performance of the prepared composite cobaltosic oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite cobaltosic oxide material is more than 90 percent after 100 cycles of 1C current.
Example 10
Dispersing 2.37g of nickel chloride hexahydrate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) for continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), performing freeze drying to obtain solid powder, and annealing at 500 ℃ for 2h in a tubular furnace to obtain the nickel oxide.
1.27g of lithium chloride was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 30 minutes to form a uniform solution, followed by 0.98g of phosphoric acid (98% by mass) was added, and stirred sufficiently for 60 minutes to form a uniform sol solution.
Taking 6.03ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of nickel oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the oligomeric lithium phosphate composite nickel oxide material. The electrochemical performance of the prepared composite nickel oxide material passes through a button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite nickel oxide material is more than 90 percent after 100 cycles of 1C current.
Example 11
Dispersing 1.97g of manganese chloride tetrahydrate in 100ml of deionized water, stirring for 30min until a solution with uniform color is formed, dropwise adding 6ml of ammonia water solution (the mass fraction is 25-28 wt%) for continuously stirring for 6h, obtaining a colloid solution with uniform color, performing solid-liquid separation by using a centrifugal machine (8000 revolutions for 5 min), performing freeze drying to obtain solid powder, and annealing in a tubular furnace at 500 ℃ for 2h to obtain manganese dioxide.
1.27g of lithium chloride was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 30 minutes to form a uniform solution, followed by 0.98g of phosphoric acid (98% by mass) was added, and stirred sufficiently for 60 minutes to form a uniform sol solution.
Taking 6.03ml of sol solution (0.02 g of oligomeric lithium phosphate) and 0.4g of manganese dioxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and drying the obtained powder in an oven for 24 hours to obtain the oligomeric lithium phosphate composite manganese dioxide material. The electrochemical performance of the prepared composite manganese dioxide material passes through a button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite manganese dioxide material for 100 circles under 1C current is more than 90 percent.
Example 12
Titanium dioxide powder synthesized using sol-gel method: 6.8ml of tetrabutyl titanate is taken and dispersed in 50ml of ethanol, deionized water is slowly added dropwise to the tetrabutyl titanate, the tetrabutyl titanate is fully hydrolyzed, and a clear solution is obtained after centrifugal cleaning and then a proper amount of nitric acid is added. 8.4g of citric acid is dissolved in deionized water according to the following citric acid: ti (Ti) 4+ The molar ratio of 2:1 is equal to the appropriate amount of Ti-containing material 4+ Mixing the clear solutions, regulating pH to 7 with ammonia water, volatilizing at 90deg.C under stirring to form gel, and annealing at 500deg.C in a tube furnace for 4 hr to obtain titanium dioxide powder.
2.07g of lithium nitrate was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 60 minutes to form a homogeneous solution, followed by 0.98g of phosphoric acid (98 wt% by mass) was added, and stirred sufficiently for 30 minutes to form a homogeneous oligomer solution.
4.31ml of oligomer solution (0.02 g of oligomer lithium phosphate) and 0.40g of titanium dioxide powder are taken, stirred at 50 ℃ until the liquid is completely volatilized, and the obtained powder is freeze-dried for 24 hours to obtain the oligomer lithium phosphate modified titanium dioxide material. The electrochemical performance of the prepared composite titanium dioxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite titanium dioxide material is more than 90 percent after 100 cycles of 1C current.
Example 13
The niobium pentoxide powder was synthesized using a hydrothermal method: putting a certain amount of niobium oxalate solution (0.01 mol/L) into a reaction kettle of 80ml, ensuring the filling degree to be about 70%, reacting for 16 hours at 180 ℃ to obtain suspension, centrifuging, freeze-drying to obtain solid powder, and annealing for 2 hours at 800 ℃ in a tubular furnace under the protection of argon to obtain the product niobium pentoxide.
2.07g of lithium nitrate was dispersed in 200ml of ethanol, 50ml of triethylamine was added, and stirred for 60 minutes to form a homogeneous solution, followed by 0.98g of phosphoric acid (98 wt% by mass) was added, and stirred sufficiently for 30 minutes to form a homogeneous oligomer solution.
Taking 4.31ml of oligomer solution (wherein the oligomer lithium phosphate is 0.02 g) and 0.40g of niobium pentoxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the oligomer lithium phosphate modified niobium pentoxide material. The electrochemical performance of the prepared composite niobium pentoxide material passes the button cell test, the voltage is between 0.01 and 3V, and the capacity retention rate of the composite niobium pentoxide material is more than 90 percent after 100 cycles of 1C current.
Example 14
The procedure for preparing the inorganic oligomer lithium-containing composite metal oxide material of example 14 is described with reference to example 1, except that: taking 6.47ml of oligomer solution (wherein the oligomer lithium phosphate is 0.03 g) and 0.40g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the oligomer lithium phosphate modified ferric oxide material. The electrochemical performance of the prepared oligomer lithium phosphate modified ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the first discharge capacity of the oligomer lithium phosphate composite ferric oxide material reaches 900mAh g -1 The capacity retention rate was greater than 90% at 500 cycles of 1C current.
Example 15
Preparation of inorganic oligomer lithium-containing composite Metal oxide Material in example 15 The procedure is as in example 1, with the difference that: 8.62ml of oligomer solution (wherein the oligomer lithium phosphate is 0.04 g) and 0.40g of ferric oxide powder are taken, the mixture is stirred at 50 ℃ until the liquid is completely volatilized, and the obtained powder is frozen and dried for 24 hours to obtain the oligomer lithium phosphate modified ferric oxide material. The electrochemical performance of the prepared oligomer lithium phosphate modified ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the first discharge capacity of the oligomer lithium phosphate composite ferric oxide material reaches 900mAh g -1 About, the capacity retention rate is greater than 90% when the 1C current is cycled for 500 circles.
Example 16
The procedure for preparing the inorganic oligomer lithium-containing composite metal oxide material of example 16 is described with reference to example 1, except that: taking 17.24ml of oligomer solution (wherein the oligomer lithium phosphate is 0.08 g) and 0.40g of ferric oxide powder, stirring at 50 ℃ until the liquid is completely volatilized, and freeze-drying the obtained powder for 24 hours to obtain the oligomer lithium phosphate modified ferric oxide material. The electrochemical performance of the prepared oligomer lithium phosphate modified ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the first discharge capacity of the oligomer lithium phosphate composite ferric oxide material reaches 600mAh g -1 The capacity retention rate was greater than 90% for 200 cycles of the above 1C current.
Example 17
The procedure for preparing the inorganic oligomer lithium-containing composite metal oxide material of example 17 is described with reference to example 1, except that: 43.10ml of oligomer solution (0.20 g of oligomer lithium phosphate) and 0.40g of ferric oxide powder are taken, stirred at 50 ℃ until the liquid is completely volatilized, and the obtained powder is frozen and dried for 24 hours to obtain the oligomer lithium phosphate modified ferric oxide material. The electrochemical performance of the prepared oligomer lithium phosphate modified ferric oxide material passes the button cell test, the voltage is between 0.01 and 3V, and the first discharge capacity of the oligomer lithium phosphate composite ferric oxide material reaches 500mAh g -1 About, the capacity retention rate is greater than 90% at 1C current cycling for 200 turns.
Comparative example 1
Commercial nano iron oxide (Fe 2 O 3 ) As a comparison sampleThe electrochemical performance of which passed the button cell test. Specifically: commercial iron oxide was oven dried at 120 ℃ for 12h, following active materials: PVDF: acetylene black=8:1:1 (mass ratio), the mixture was weighed and smeared, then dried in vacuo at 90 ℃, cut into pole pieces with a diameter of about 12mm, and the assembled battery was left to stand for 12 hours and then subjected to various electrochemical performance tests. As can be seen from fig. 5, the discharge capacity of the present comparative example 1 and the cyclic discharge capacity at 1C under the test conditions of different magnifications were lower than those of the oligomeric lithium phosphate composite iron oxide material prepared in example 1.
Claims (7)
1. The inorganic oligomer lithium-containing compound metal oxide material used as the negative electrode material of the lithium ion battery is characterized in that the outer layer of the inorganic oligomer lithium-containing compound metal oxide material is an inorganic oligomer lithium-containing material with an amorphous structure, and the inner layer is a metal oxide;
the mass ratio of the metal oxide to the inorganic oligomer lithium content is 1: (0.01-0.5);
the structural general formula of the metal oxide is N u O v Wherein N is selected from at least one of iron element, cobalt element, manganese element, nickel element, titanium element and niobium element, and u is more than or equal to 1 and less than or equal to 3, v is more than or equal to 1 and less than or equal to 4;
the structural general formula of the inorganic oligomer lithium-containing material is Li x MO y Wherein M is at least one of phosphorus element, silicon element, boron element and aluminum element, x is more than or equal to 1 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 5;
the size of the inorganic oligomer lithium-containing compound metal oxide material is 0.1-20 mu m, and the specific surface area is more than 210m 2 /g；
The size of the metal oxide is 100 nm-20 mu m; the metal oxide is secondary particles formed by stacking primary particles, and the size of the primary particles is 10 nm-1 mu m;
the preparation method of the inorganic oligomer lithium-containing compound metal oxide material comprises the following steps:
dispersing soluble lithium salt in ethanol, adding triethylamine, fully stirring, then dropwise adding at least one of soluble phosphorus, boron, silicon and aluminate, and stirring uniformly to obtain a solution of inorganic oligomer lithium-containing substances; the mole ratio of the soluble lithium salt to triethylamine is 1: (6-100); the mole ratio of the soluble lithium salt to the soluble phosphate, boron, silicon and aluminate is (1-3): (1-5);
Metal oxide N u O v Adding the solid powder into the solution of the inorganic oligomer lithium-containing material, rapidly stirring until the liquid is completely volatilized, and drying to obtain the inorganic oligomer lithium-containing material composite metal oxide material; the metal oxide N u O v The mass ratio of the inorganic oligomer to the inorganic oligomer lithium-containing material is 1: (0.01-0.5); the temperature of the stirring is 60-80 ℃.
2. The inorganic oligomer lithium-containing composite metal oxide material of claim 1, wherein the mass ratio of metal oxide to inorganic oligomer lithium-containing is 1: (0.01-0.1).
3. The inorganic oligomer lithium-containing composite metal oxide material of claim 1, wherein the inorganic oligomer lithium-containing material is lithium phosphate and the metal oxide is iron oxide.
4. The inorganic oligomer lithium-containing composite metal oxide material of claim 1, wherein the primary particle size is from 10nm to 500nm.
5. The inorganic oligomer lithium-containing composite metal oxide material according to claim 1, wherein the inorganic oligomer lithium-containing material is a lithium compound formed by repeating covalent bonding of monomers + And MO (metal oxide semiconductor) y -z The number of monomers is less than or equal to 20.
6. The inorganic oligomer lithium-containing composite metal oxide material of claim 1, wherein the molar ratio of soluble lithium salt to triethylamine is 1: (8-100); the mole ratio of the soluble lithium salt to the soluble phosphate, boron, silicon and aluminate is (2-3): 1.
7. The inorganic oligomer lithium-containing composite metal oxide material of claim 1, wherein the soluble lithium salt is at least one of lithium chloride, lithium nitrate, lithium sulfate, lithium hydroxide; the soluble phosphorus, boron, silicon and aluminate is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, silicic acid, boric acid, metaboric acid, aluminate and the like.
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