CN104037407B - A kind of cobalt acid lithium composite of lithium superionic conductors cladding and preparation method thereof - Google Patents
A kind of cobalt acid lithium composite of lithium superionic conductors cladding and preparation method thereof Download PDFInfo
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- CN104037407B CN104037407B CN201410219058.5A CN201410219058A CN104037407B CN 104037407 B CN104037407 B CN 104037407B CN 201410219058 A CN201410219058 A CN 201410219058A CN 104037407 B CN104037407 B CN 104037407B
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- Prior art keywords
- lithium
- cobalt acid
- superionic conductors
- acid lithium
- cladding
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 228
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 141
- 239000010941 cobalt Substances 0.000 title claims abstract description 141
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000002253 acid Substances 0.000 title claims abstract description 131
- 239000002226 superionic conductor Substances 0.000 title claims abstract description 86
- 238000005253 cladding Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 230000014759 maintenance of location Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 14
- 235000011285 magnesium acetate Nutrition 0.000 claims description 14
- 239000011654 magnesium acetate Substances 0.000 claims description 14
- 229940069446 magnesium acetate Drugs 0.000 claims description 14
- 159000000003 magnesium salts Chemical class 0.000 claims description 14
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 8
- 239000002671 adjuvant Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 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 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 claims description 5
- -1 phosphate ester Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 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 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910015353 LiMgPO4 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of cobalt acid lithium composite of lithium superionic conductors cladding and preparation method thereof.Using mixing oxides method and precipitation cladding process in stratiform cobalt acid lithium Surface coating lithium superionic conductors, lithium superionic conductors is formed in cobalt acid lithium particle surface and is uniformly coated by the stratiform that little particle is constituted the present invention.When higher temperature is calcined, part lithium superionic conductors is reacted with cobalt acid lithium, and the metallic element in lithium superionic conductors is entrained in cobalt acid lithium surface, and the phosphate radical in lithium superionic conductors is combined generation Li with the lithium in cobalt acid lithium3PO4, above-mentioned reaction to reduce sheet resistance, improve cyclical stability it is favourable.After in the case where cobalt acid lithium granule is moderate, there is higher specific capacity and cycle charge discharge electrical stability, experimental cell test to show that the cobalt acid lithium material is circulated discharge and recharge 50 weeks under 4.6V, 0.7C/0.7C electric current density for which, its capability retention is more than 90%.
Description
Technical field
The invention belongs to lithium ion battery electrode material field, is related to a kind of cobalt acid lithium of lithium superionic conductors cladding and is combined
Material and preparation method thereof.
Background technology
Cobalt acid lithium has higher capacity, discharge platform and compacted density, is that research is the most abundant, most widely used at present
Commercial Li-ion battery positive electrode.In lithium ion battery charge and discharge process, the cobalt acid lithium of single-phase is used as positive pole material
Material and electrolyte directly contact, the dissolution phenomenon that cobalt by electrolytic corrosion, can occur, original layer structure is destroyed, and oxygen
Change and decompose electrolyte, ultimately result in the rapid decay of material capacity, or even the safety problems such as burning, blast occur.In cobalt acid lithium
Surface coating other materials, can efficiently reduce the contact area of cobalt acid lithium and electrolyte, reduce Co stripping quantities, improve structure
Stability and cycle performance.
Common covering material is metal-oxide, for example MgO, ZnO, A12O3、La2O3、TiO2、ZrO2Deng this kind of material
Stability Analysis of Structures, will not be reacted with electrolyte, serve the effect of protection cobalt acid lithium.Yong Jeong Kim et al.
[Chem.Mater.2003,15,1505-1511] one layer is about 30nm thickness in cobalt acid lithium Surface coating using reactive sputtering
A12O3, Electrochemical results display A12O3The cobalt acid lithium of cladding compared with uncoated cobalt acid lithium, half-cell 2.75～
There is in the cyclic process of 4.4V more preferable structural stability and capability retention, but 80 weeks before circulation, A12O3Cladding
The lithium ion diffusion coefficient of cobalt acid lithium is less than uncoated cobalt acid lithium.AlPO4、FePO4、Li3PO4、LiMgPO4Also may be used Deng phosphate
Using the covering material as cobalt acid lithium.Jaephil Cho et al. [Journal of Power Sources, 2005,146,58-
64] AlPO is prepared for using precipitation cladding process4The cobalt acid lithium of cladding, with uncoated cobalt acid lithium and A12O3The cobalt acid lithium phase of cladding
Than, in the cyclic process of 3.0～4.5V of half-cell, AlPO4The cobalt acid lithium of cladding has more preferable structural stability and capacity
Conservation rate, the lithium ion diffusion coefficient and heat stability highest under Charging state.This is because AlPO4Have in structure it is open from
Sub- transmission channel, the structural framework being made up of a phosphonium ion and four oxonium ions are highly stable.
In recent years, the lithium superionic conductors with sodium superionic conductors structure is generally studied as solid electrolyte, because
There is higher lithium ion conductivity and stable crystal structure for this kind of material.The patent of Yin Yanhong et al.
[CN102738451A, CN102760884A] shows that lithium superionic conductors cladding can improve the table of anode material for lithium-ion batteries
Face electric conductivity, improves capability retention and cycle performance.Hideyuki Morimoto et al. [Journal of Power
Sources, 2013,240,636-643] Li is prepared by the way of ball milling mixing1.3Al0.3Ti1.7(PO4)3The cobalt acid lithium of cladding,
Compared with the cobalt acid lithium that non-surface is modified, Li1.3Al0.3Ti1.7(PO4)3The sheet resistance of the cobalt acid lithium of cladding is less, in half-cell
In the cyclic process of 3.0～4.5V, more preferable capability retention and cycle performance are shown.
The content of the invention
It is an object of the invention to provide a kind of cobalt acid lithium composite of lithium superionic conductors cladding and preparation method thereof, adopts
With lithium superionic conductors LicMgdTieM′f(PO4)3Cladding improves the lithium ion conduction performance on cobalt acid lithium surface, makes preparation of the present invention
Cobalt acid lithium composite there is under 4.5V even more high voltages good cycle performance and structural stability.
To achieve these goals, the present invention is employed the following technical solutions：
A kind of cobalt acid lithium composite of lithium superionic conductors cladding, coats cobalt acid lithium material shape by lithium superionic conductors
Into its chemical formula is (1-x) Li1+aCo1-bMbO2·xLicMgdTieM′f(PO4)3, wherein 0<x≤0.1.The cobalt acid lithium being wrapped by
Material is layer structure, and chemical formula is Li1+aCo1-bMbO2, wherein 0≤a≤0.1,0<B≤0.1, M be Mg, Ca, Cu, Ni, Al,
One or more in Sc, Fe, Y, Ti, Mn, Zr, V, Nb.The chemical formula of described lithium superionic conductors is LicMgdTieM′f
(PO4)3, wherein 0≤c≤1,0<D≤1,0<E≤2,0≤f≤2, M ' be Na, Mg, Ca, Cu, Ni, Al, Sc, Fe, Y, Mn, Zr,
One or more in V, Nb, 1 × c+2 × d+4 × e+n × f=12, n are the average valences of M '.
Further, the described cobalt acid lithium material being wrapped by is prepared using solid phase method, and the particle size range of granule is 2
～20 μm.The preparation method of described lithium superionic conductors includes solid phase mixing sintering process, liquid-phase precipitation sintering process.Described lithium
The preparation method of the cobalt acid lithium composite of superionic conductors cladding includes mixing oxides method and precipitation cladding process.
The method that mixing oxides method prepares the cobalt acid lithium composite of lithium superionic conductors cladding is as follows：
1) the molar ratio weighing lithium source of element shown in the chemical formula by the cobalt acid lithium material being wrapped by, cobalt source and containing M it is first
Then the adjuvant of element, mix homogeneously is calcined at 850～1100 DEG C, and temperature retention time is 2～10 hours, and cobalt is obtained after natural cooling
Sour powder for lithium.
2) butyl titanate is dissolved in ethanol by the mol ratio of element shown in the chemical formula by lithium superionic conductors, will
Lithium salts, magnesium salt, the raw material containing M ' elements, phosphorus source are dissolved in ethanol respectively, are stirred.Mixing butyl titanate, lithium salts, magnesium
After the solution of salt, the raw material containing M ' elements and phosphorus source, stirring 0.5～2 hour, it is heated to 50～80 DEG C of stirrings and is evaporated, 80～
It is dried 8～24 hours in 120 DEG C of baking oven, obtains the presoma of lithium superionic conductors.
3) by step 2) in the presoma of lithium superionic conductors that obtains calcine at 300～1100 DEG C, temperature retention time is 1～
10 hours, after natural cooling, obtain lithium superionic conductors.
4) by step 3) in the lithium superionic conductors that obtains and step 1) in the cobalt acid lithium powder body mix homogeneously that obtains, then
Calcine at 500～1100 DEG C, temperature retention time is 1～10 hour, after natural cooling, obtain the cobalt acid lithium of lithium superionic conductors cladding
Composite.
Step 1) described in lithium source be lithium carbonate, one or two the mixture in Lithium hydrate, the cobalt source is four
The mixture of one or more in Co 3 O, hydroxy cobalt oxide, cobalt hydroxide, the adjuvant containing M element are the oxidations of M
The mixture of one or more in thing, hydroxide, acetate, carbonate, subcarbonate.
Step 1) in, the particle size range of the cobalt acid lithium powder granule is 2～20 μm.
Step 2) described in the w/v (g/mL) of butyl titanate and ethanol be 1 (g):5 (mL)～1 (g):100
(mL), described lithium salts be lithium nitrate, Quilonorm (SKB), one or more in Lithium hydrate of mixture, described magnesium salt is nitre
One or two mixture in sour magnesium, magnesium acetate, the raw material containing M ' elements are the nitrate of metallic element M ', acetic acid
The mixture of one or more in salt, chloride, oxychlorination things, organic salt, phosphorus source are ammonium dihydrogen phosphate, biphosphate
The mixing of one or more in lithium, diammonium phosphate, phosphoric acid, phosphate ester (including mono-organic phosphate, di-phosphate ester, phosphotriester)
Thing.The concentration of the solution of the lithium salts, magnesium salt, the raw material containing M ' elements and phosphorus source is 0.01～1mol/L respectively.
Preferably, step 3) described in calcining heat be 500～800 DEG C, step 4) described in calcining heat be 700～
1000℃。
Preferably, step 4) described in lithium superionic conductors weight less than the lithium superionic conductors cladding cobalt acid
The 5% of lithium composite material gross weight.
The method that liquid-phase precipitation method prepares the cobalt acid lithium composite of lithium superionic conductors cladding is as follows：
1) the molar ratio weighing lithium source of element shown in the chemical formula by the stratiform cobalt acid lithium being wrapped by, cobalt source and containing M it is first
Then the adjuvant of element, mix homogeneously are calcined 2～10 hours at 850～1100 DEG C, cobalt acid lithium powder body are obtained after natural cooling.
2) butyl titanate is dissolved in ethanol by the mol ratio of element shown in the chemical formula by lithium superionic conductors, will
Lithium salts, magnesium salt, the raw material containing M ' elements, phosphorus source are dissolved in ethanol respectively, are stirred.Dry cobalt acid lithium powder body is poured into
In ethanol, dispersed with stirring is uniform.
3) first to step 2) in cobalt acid lithium suspension in add lithium salts, magnesium salt, the raw material containing M ' elements, butyl titanate
Solution, stirs, then is added thereto to phosphorus source solution, after stirring 0.5～2 hour, the forerunner of the lithium superionic conductors of generation
Body is coated on powder surface, is then heated to 50～80 DEG C of stirrings and is evaporated, in 80～120 DEG C of baking ovens dry solids 8～
24 hours, obtain the cobalt acid lithium powder body of lithium superionic conductors presoma cladding.
4) by step 3) in obtain lithium superionic conductors presoma cladding cobalt acid lithium powder body forge at 500～1100 DEG C
Burn, temperature retention time is 1～10 hour, after natural cooling, obtain the cobalt acid lithium material of lithium superionic conductors cladding.
Step 1) described in lithium source be lithium carbonate, one or two the mixture in Lithium hydrate, the cobalt source is four
The mixture of one or more in Co 3 O, hydroxy cobalt oxide, cobalt hydroxide, the adjuvant containing M element are the oxidations of M
The mixture of one or more in thing, hydroxide, acetate, carbonate, subcarbonate.
Step 1) in, the particle size range of the cobalt acid lithium powder granule is 2～20 μm.
Step 2) described in the volume ratio of butyl titanate and ethanol be 1:5～1:100, described lithium salts is nitric acid
The mixture of one or more in lithium, Quilonorm (SKB), Lithium hydrate, described magnesium salt is magnesium nitrate, the one kind in magnesium acetate or
Two kinds of mixture, the raw material containing M ' elements are the nitrate of metallic element M ', acetate, chloride, oxychlorination things, have
The mixture of one or more in machine salt, described phosphorus source be ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium phosphate, phosphoric acid,
The mixture of one or more in phosphate ester (including mono-organic phosphate, di-phosphate ester, phosphotriester).The lithium salts, magnesium salt, contain
The concentration of the solution that the raw material of M ' elements, phosphorus source dissolving are formed in ethanol is 0.01～1mol/L respectively.
Preferably, step 3) described in lithium superionic conductors cladding weight less than material gross weight 5%.
Preferably, step 4) described in calcining heat be 700～1000 DEG C.
The present invention adopts lithium superionic conductors LicMgdTieM′f(PO4)3Cladding improves the lithium ion conduction on cobalt acid lithium surface
Performance, makes cobalt acid lithium have more preferable cycle performance under 4.5V even more high voltages.LicMgdTieM′f(PO4)3As cladding
Material with performance of both aggregate balancing lithium ion conductivity and structural stability, can play the work of preferably protection body
With.When calcining in higher temperature, part LicMgdTieM′f(PO4)3Can react with cobalt acid lithium, reduce between clad and body
Interface, beneficial to lithium ion transport.After pyroreaction, Mg, Ti, M ' are entrained in cobalt acid lithium surface, play raising surface conductance
The effect of rate, while generating Li3PO4, it is same to have and higher lithium ion conductivity and preferable corrosion resistance.
The method that the present invention is provided need to only pass through stirring mixing and heat treated is obtained lithium superionic conductors cladding
Cobalt acid lithium material, the purity of lithium superionic conductors is higher, coat and must require low, the charge and discharge of product to Preparation equipment than more uniform
Electric cycle performance is substantially better than the cobalt acid lithium material of cladding before processing.
Description of the drawings
Fig. 1 is the X-ray diffraction spectrogram after the lithium superionic conductors of embodiment 5 in the present invention is calcined 1 hour at 1000 DEG C.
Fig. 2 is the field emission scanning electron microscope photo of the Surface coating pattern of embodiment 5 in the present invention；
Fig. 3 is the high resolution transmission electron microscopy photo of the Surface coating pattern of embodiment 5 in the present invention；
Fig. 4 be in the present invention embodiment 5 in half-cell 3.0～4.6V through obtained by 0.2C/0.2C charge-discharge tests
Specific capacity-voltage curve；
Fig. 5 is uncoated cobalt acid lithium and embodiment 4, embodiment 5, the cobalt acid lithium material of the preparation of embodiment 6 in half-cell
In 3.0～4.6V, high rate performance curve obtained by 0.2C/0.5C/1C charge-discharge tests；
Fig. 6 is uncoated cobalt acid lithium and embodiment 4, embodiment 5, the cobalt acid lithium material of the preparation of embodiment 6 in half-cell
In under the conditions of 3.0～4.6V, 0.7C/0.7C through the specific capacity obtained by charge-discharge test-cycle-index curve.
Specific embodiment：
Illustrate the present invention below by way of example, but be not construed as limiting the invention.
Embodiment 1
According to chemical formula Li1.05Co0.97Mg0.02Al0.01O2Mol ratio weigh lithium carbonate, Cobalto-cobaltic oxide, magnesium oxide and
Aluminium oxide is placed in ball grinder, and the mass ratio of ball material is 1.5:1, ball milling 6 hours, mix homogeneously.Calcined mixed powder body, calcining temperature
Spend for 950 DEG C, temperature retention time is 8 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Li0.8Mg0.1Ti0.1Zr1.8Mn0.1(PO4)3Mol ratio weigh butyl titanate, tetrabutyl zirconate
It is dissolved in 10mL, 50mL ethanol respectively, is stirred.Quilonorm (SKB), magnesium acetate, manganese acetate, diammonium phosphate difference are weighed again
It is dissolved in a small amount of ethanol, stirs.First to Deca butyl titanate, tetrabutyl zirconate solution in ammonium dibasic phosphate solution,
Deca Quilonorm (SKB), magnesium acetate, acetic acid manganese solution, then stir 2 hours again.Mixed liquor is heated to into 50 DEG C, stirring is evaporated, then
It is put into 80 DEG C of oven dryings 20 hours.The dry powder body of calcining, calcining heat are 800 DEG C, and temperature retention time is 6 hours, naturally cold
But lithium superionic conductors is obtained afterwards.
By lithium superionic conductors and cobalt acid lithium powder body ball milling mixing 4 hours, then calcined mixed was uniform in air atmosphere
Powder body, calcining heat be 1000 DEG C, temperature retention time be 2 hours, obtain after natural cooling 5% lithium superionic conductors cladding cobalt
Sour lithium material.
Embodiment 2
According to chemical formula Li1.10Co0.94Al0.02Ti0.04O2Mol ratio weigh Lithium hydrate, hydroxy cobalt oxide, hydroxide
Aluminum and titanium dioxide are placed in mixing tank, and the mass ratio of ball material is 2:1, mixed 6 hours with three-dimensional material mixer, mix homogeneously.Forge
Mixed powder is burnt, calcining heat is 1100 DEG C, and temperature retention time is 2 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Li0.1Mg0.2Ti1.6V0.4Na0.1(PO4)3Mol ratio weigh butyl titanate and be dissolved in 30mL second
In alcohol, stir.Lithium nitrate, magnesium nitrate, sodium nitrate, ammonium metavanadate, ammonium dihydrogen phosphate are weighed again is dissolved in a small amount of second respectively
In alcohol, stir.First to Deca ammonium dihydrogen phosphate in tetrabutyl zirconate solution, then Deca lithium nitrate, magnesium nitrate, nitric acid
Sodium, ammonium metavanadate solution, then stir 0.5 hour.Mixed liquor is heated to into 80 DEG C, stirring is evaporated, is then placed in 120 DEG C of baking ovens
It is dried 8 hours.The dry powder body of calcining, calcining heat are 500 DEG C, and temperature retention time is 1 hour, obtain after natural cooling lithium surpass from
Sub- conductor.
By lithium superionic conductors and cobalt acid lithium powder body ball milling mixing 4 hours, the then uniform powder body of calcined mixed, calcining temperature
Spend for 700 DEG C, temperature retention time is 1 hour, after natural cooling, obtain the cobalt acid lithium material of 5% lithium superionic conductors cladding.
Embodiment 3
According to chemical formula Li1.01Co0.99Mg0.005Zr0.005O2Mol ratio weigh Lithium hydrate, cobalt hydroxide, alkali formula carbon
Sour magnesium and zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling mixing 4 hours.The uniform powder of calcined mixed
Body, calcining heat are 1000 DEG C, and temperature retention time is 6 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Mg0.9TiYNi0.1(PO4)3Mol ratio weigh butyl titanate and be dissolved in 20mL ethanol, stir
Uniformly.Weigh magnesium acetate, Yttrium trinitrate, nickel acetate, diammonium phosphate to be dissolved in a small amount of ethanol respectively, stir.To phosphoric acid
Deca butyl titanate, magnesium acetate, Yttrium trinitrate, Ni-acetate solution in two ammonium salt solution of hydrogen, then stir 1.5 hours.By mixed liquor
70 DEG C are heated to, stirring is evaporated, are then placed in 110 DEG C of oven dryings 12 hours.The dry powder body of calcining, calcining heat is 700
DEG C, temperature retention time is 10 hours, and lithium superionic conductors is obtained after natural cooling.
Lithium superionic conductors is mixed with cobalt acid lithium powder body, is mixed 4 hours with three-dimensional material mixer, then calcined mixed is uniform
Powder body, calcining heat be 900 DEG C, temperature retention time be 10 hours, obtain after natural cooling 5% lithium superionic conductors cladding cobalt
Sour lithium material.
Embodiment 4
According to chemical formula Li1.06Co0.90Ni0.05Mn0.05O2Mol ratio weigh lithium carbonate, cobalt hydroxide, nickel hydroxide and
Manganous hydroxide is placed in ball grinder, and the mass ratio of ball material is 1.5:1, ball milling mixing 6 hours.The uniform powder body of calcined mixed, forges
It is 850 DEG C to burn temperature, and temperature retention time is 10 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Li0.5Mg0.5Ti1.5Al0.5(PO4)3Mol ratio weigh butyl titanate and be dissolved in 10mL ethanol
In, stir.Weigh Lithium hydrate, magnesium acetate, aluminum nitrate, lithium dihydrogen phosphate to be dissolved in a small amount of ethanol respectively, stirring is equal
It is even.The cobalt acid lithium powder body for preparing before is poured in 200mL ethanol, dispersed with stirring 30min, first four fourth of Deca metatitanic acid thereto
Ester, Quilonorm (SKB), magnesium acetate, aluminum nitrate solution, then Deca lithium dihydrogen phosphate solution, then stir 1 hour.Mixed liquor is heated to
60 DEG C, stirring is evaporated, and is then placed in 100 DEG C of oven dryings 10 hours.The dry powder body of calcining, calcining heat are 1000 DEG C, are protected
The warm time is 4 hours, and the cobalt acid lithium material of 1% lithium superionic conductors cladding is obtained after natural cooling.
Embodiment 5
According to chemical formula Li1.06Co0.90Ni0.05Mn0.05O2Mol ratio weigh lithium carbonate, cobalt hydroxide, nickel hydroxide and
Manganous hydroxide is placed in ball grinder, and the mass ratio of ball material is 1.5:1, ball milling mixing 6 hours.The uniform powder body of calcined mixed, forges
It is 850 DEG C to burn temperature, and temperature retention time is 10 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Li0.5Mg0.5Ti1.5Al0.5(PO4)3Mol ratio weigh butyl titanate and be dissolved in 30mL ethanol
In, stir.Weigh Lithium hydrate, magnesium acetate, aluminum nitrate, lithium dihydrogen phosphate to be dissolved in a small amount of ethanol respectively, stirring is equal
It is even.The cobalt acid lithium powder body for preparing before is poured in 200mL ethanol, dispersed with stirring 30min, first four fourth of Deca metatitanic acid thereto
Ester, Quilonorm (SKB), magnesium acetate, aluminum nitrate solution, then Deca lithium dihydrogen phosphate solution, then stir 1 hour.Mixed liquor is heated to
60 DEG C, stirring is evaporated, and is then placed in 100 DEG C of oven dryings 10 hours.The dry powder body of calcining, calcining heat are 1000 DEG C, are protected
The warm time is 4 hours, and the cobalt acid lithium material of 3% lithium superionic conductors cladding is obtained after natural cooling.
The presoma of the lithium superionic conductors in the embodiment 1000 DEG C calcining 1 hour after X-ray diffraction spectrogram such as
Shown in Fig. 1, diffraction maximum therein belongs to lithium superionic conductors substantially, and impurity peaks very little illustrates that impurity content is little.The cobalt acid
The field emission scanning electron microscope photo of the Surface coating pattern of lithium material is as shown in Fig. 2 after 1000 DEG C of calcinings, part lithium surpasses
Ion conductor is reacted with cobalt acid lithium, is incorporated in cobalt acid lithium, and surface topography compares uniformity.The high-resolution of Surface coating pattern is saturating
(amplification is 10 × 10 as shown in Figure 3 to penetrate electron micrograph3Times, scale is 200nm), after 1000 DEG C of calcinings, part
Lithium superionic conductors is not reacted with cobalt acid lithium, forms the clad of nanoscale little particle composition on cobalt acid lithium surface.
Embodiment 6
According to chemical formula Li1.06Co0.90Ni0.05Mn0.05O2Mol ratio weigh lithium carbonate, cobalt hydroxide, nickel hydroxide and
Manganous hydroxide is placed in ball grinder, and the mass ratio of ball material is 1.5:1, ball milling mixing 6 hours.The uniform powder body of calcined mixed, forges
It is 850 DEG C to burn temperature, and temperature retention time is 10 hours, and 100g cobalt acid lithium powder body is obtained after natural cooling.
According to chemical formula Li0.5Mg0.5Ti1.5Al0.5(PO4)3Mol ratio weigh butyl titanate and be dissolved in 50mL ethanol
In, stir.Weigh Lithium hydrate, magnesium acetate, aluminum nitrate, lithium dihydrogen phosphate to be dissolved in a small amount of ethanol respectively, stirring is equal
It is even.The cobalt acid lithium powder body for preparing before is poured in 200mL ethanol, dispersed with stirring 30min, first four fourth of Deca metatitanic acid thereto
Ester, Quilonorm (SKB), magnesium acetate, aluminum nitrate solution, then Deca lithium dihydrogen phosphate solution, then stir 1 hour.Mixed liquor is heated to
60 DEG C, stirring is evaporated, and is then placed in 100 DEG C of oven dryings 10 hours.The dry powder body of calcining, calcining heat are 1000 DEG C, are protected
The warm time is 4 hours, and the cobalt acid lithium material of 5% lithium superionic conductors cladding is obtained after natural cooling.
The evaluation methodology of the electrical property of the cobalt acid lithium material for lithium superionic conductors cladding used of the invention is as follows：
The cobalt acid lithium material that the lithium superionic conductors is coated is with conductive carbon black and binding agent Vingon according to matter
Amount compares 90:5:5 ratio is mixed, and Deca N-Methyl pyrrolidone is ground to pasty state and is coated in aluminium foil surface, 120 DEG C of bakings
Positive pole test electrode is obtained after dry.Select to electrode (reference electrode) metal lithium sheet, experimental cell of experimental cell is selected
CR2032 type battery components are assembled, and experimental cell is placed in calorstat and connects charge-discharge test instrument and is circulated charge and discharge electrical measurement
Examination.
Wherein, embodiment 5 prepare cobalt acid lithium material in half-cell 3.0～4.6V through 0.2C/0.2C charge and discharge electrical measurements
Specific capacity-the voltage curve of examination gained, as shown in figure 4, the specific discharge capacity of this material reaches 220mAh/g, discharge platform is high
In 3.9V, polarize very little.
The cobalt acid lithium material that uncoated cobalt acid lithium is prepared with embodiment 4, embodiment 5, embodiment 6 is 3.0 in half-cell
～4.6V, high rate performance curve obtained by 0.2C/0.5C/1C charge-discharge tests are as shown in figure 5, embodiment 4, embodiment 5, embodiment
The high rate performance of the 6 cobalt acid lithium materials for preparing all is higher than uncoated cobalt acid lithium, the cobalt acid lithium material tool that wherein prepared by embodiment 5
There is best high rate performance.The above results explanation lithium superionic conductors cladding can improve the high rate performance of cobalt acid lithium, but coat
Amount can not be excessive.
The cobalt acid lithium material that uncoated cobalt acid lithium is prepared with embodiment 4, embodiment 5, embodiment 6 is 3.0 in half-cell
Through the specific capacity obtained by charge-discharge test-cycle-index curve under the conditions of～4.6V, 0.7C/0.7C, as shown in fig. 6, implementing
The cycle performance of cobalt acid lithium material prepared by example 4, embodiment 5, embodiment 6 is all higher than uncoated cobalt acid lithium, wherein embodiment 5
The cobalt acid lithium material of preparation has best cycle performance (after cycle charge-discharge 50 weeks, its capability retention is more than 90%).
The above results explanation lithium superionic conductors cladding can improve the cycle performance of cobalt acid lithium, but covering amount can not be excessive.
Claims (10)
1. a kind of cobalt acid lithium composite of lithium superionic conductors cladding, is formed by lithium superionic conductors cladding cobalt acid lithium material,
Its chemical formula is (1-x) Li1+aCo1-bMbO2·xLicMgdTieM′f(PO4)3, wherein 0<x≤0.1；The cobalt acid lithium material being wrapped by
It is layer structure, chemical formula is Li1+aCo1-bMbO2, wherein 0≤a≤0.1,0<B≤0.1, M be Mg, Ca, Cu, Ni, Al, Sc,
One or more in Fe, Y, Ti, Mn, Zr, V, Nb；The chemical formula of described lithium superionic conductors is LicMgdTieM′f
(PO4)3, wherein 0≤c≤1,0<D≤1,0<E≤2,0≤f≤2, M ' be Na, Mg, Ca, Cu, Ni, Al, Sc, Fe, Y, Mn, Zr,
One or more in V, Nb；1 × c+2 × d+4 × e+n × f=9, n are the average valences of M '.
2. the preparation method of the cobalt acid lithium composite of the lithium superionic conductors cladding described in claim 1, it is characterised in that logical
The cobalt acid lithium composite that mixing oxides method prepares lithium superionic conductors cladding is crossed, is comprised the steps：
1) the molar ratio weighing lithium source of element shown in the chemical formula by the cobalt acid lithium material being wrapped by, cobalt source and containing M element
Then adjuvant, mix homogeneously is calcined at 850～1100 DEG C, and temperature retention time is 2～10 hours, and cobalt acid lithium is obtained after natural cooling
Powder body；
2) mol ratio of element shown in the chemical formula by lithium superionic conductors dissolves butyl titanate in ethanol, by lithium
Salt, magnesium salt, the raw material containing M ' elements, phosphorus source are dissolved in ethanol respectively, are stirred；Mixing butyl titanate, lithium salts, magnesium
After the solution of salt, the raw material containing M ' elements and phosphorus source, stirring 0.5～2 hour, it is heated to 50～80 DEG C of stirrings and is evaporated, 80～
It is dried 8～24 hours in 120 DEG C of baking oven, obtains the presoma of lithium superionic conductors；
3) by step 2) in the presoma of lithium superionic conductors that obtains calcine at 300～1100 DEG C, temperature retention time is 1～10 little
When, lithium superionic conductors is obtained after natural cooling；
4) by step 3) in the lithium superionic conductors that obtains and step 1) in the cobalt acid lithium powder body mix homogeneously that obtains, Ran Hou
500～1100 DEG C of calcinings, temperature retention time is 1～10 hour, and the cobalt acid lithium that lithium superionic conductors cladding is obtained after natural cooling is multiple
Condensation material.
3. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 2 cladding, it is characterised in that
Step 1) described in lithium source be lithium carbonate, one or two the mixture in Lithium hydrate, the cobalt source be Cobalto-cobaltic oxide,
The mixture of one or more in hydroxy cobalt oxide, cobalt hydroxide, the adjuvant containing M element are the oxide of M, hydroxide
The mixture of one or more in thing, acetate, carbonate, the particle size range of the cobalt acid lithium powder granule is 2～20 μm.
4. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 2 cladding, it is characterised in that
Step 2) in, the weight of the butyl titanate is 1 with the ratio of the volume of ethanol:5～1:100；Described lithium salts be lithium nitrate,
The mixture of one or more in Quilonorm (SKB), Lithium hydrate, described magnesium salt is magnesium nitrate, one or two in magnesium acetate
Mixture, the raw material containing M ' elements is the nitrate of metallic element M ', acetate, chloride, oxychlorination things, organic salt
In one or more of mixture, phosphorus source is ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium phosphate, phosphoric acid, phosphate ester
In one or more of mixture；The concentration of the solution of the lithium salts, magnesium salt, the raw material containing M ' elements and phosphorus source is 0.01
～1mol/L.
5. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 2 cladding, it is characterised in that
Step 3) described in calcining heat be 500～800 DEG C, step 4) described in calcining heat be 700～1000 DEG C.
6. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 2 cladding, it is characterised in that
Step 4) in, the weight of the lithium superionic conductors is less than the cobalt acid lithium composite gross weight that the lithium superionic conductors is coated
The 5% of amount.
7. the preparation method of the cobalt acid lithium composite of the lithium superionic conductors cladding described in claim 1, it is characterised in that logical
The cobalt acid lithium composite that liquid-phase precipitation method prepares lithium superionic conductors cladding is crossed, is comprised the steps：
1) the molar ratio weighing lithium source of element shown in the chemical formula by the stratiform cobalt acid lithium being wrapped by, cobalt source and containing M element
Then adjuvant, mix homogeneously are calcined 2～10 hours at 850～1100 DEG C, cobalt acid lithium powder body are obtained after natural cooling；
2) butyl titanate dissolving is obtained titanium by the mol ratio of element shown in the chemical formula by lithium superionic conductors in ethanol
Sour four butyl ester ethanol solution, lithium salts, magnesium salt, the raw material containing M ' elements, phosphorus source are dissolved respectively and obtain corresponding second in ethanol
Alcoholic solution, stirs, and dry cobalt acid lithium powder body is poured in ethanol, and dispersed with stirring uniformly obtains cobalt acid lithium suspension；
3) first to step 2) in cobalt acid lithium suspension in add lithium salts, magnesium salt, the raw material containing M ' elements, butyl titanate molten
Liquid, stirs, then is added thereto to phosphorus source solution, after stirring 0.5～2 hour, the presoma of the lithium superionic conductors of generation
Powder surface is coated on, 50～80 DEG C of stirrings is then heated to and is evaporated, the dry solids 8～24 in 80～120 DEG C of baking ovens
Hour, obtain the cobalt acid lithium powder body of lithium superionic conductors presoma cladding；
4) by step 3) in obtain lithium superionic conductors presoma cladding cobalt acid lithium powder body 500～1100 DEG C calcine, protect
The warm time is 1～10 hour, and the cobalt acid lithium material of lithium superionic conductors cladding is obtained after natural cooling.
8. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 7 cladding, it is characterised in that
Step 1) in, the lithium source is lithium carbonate, one or two the mixture in Lithium hydrate, and the cobalt source is four oxidations three
The mixture of one or more in cobalt, hydroxy cobalt oxide, cobalt hydroxide, the adjuvant containing M element are the oxide of M, hydrogen
The mixture of one or more in oxide, acetate, carbonate；The particle size range of the cobalt acid lithium powder granule is 2～
20μm。
9. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 7 cladding, it is characterised in that
Step 2) in, the butyl titanate is 1 with the volume ratio of ethanol:5～1:100, described lithium salts be lithium nitrate, Quilonorm (SKB),
The mixture of one or more in Lithium hydrate, described magnesium salt is magnesium nitrate, one or two the mixing in magnesium acetate
Thing, the raw material containing M ' elements be the nitrate of metallic element M ', acetate, chloride, oxychlorination things, in organic salt one
Kind or various mixture, described phosphorus source be ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium phosphate, phosphoric acid, in phosphate ester
One or more of mixture, the solution that the lithium salts, magnesium salt, the raw material containing M ' elements, phosphorus source dissolving are formed in ethanol
Concentration is 0.01～1mol/L.
10. the preparation method of the cobalt acid lithium composite of lithium superionic conductors as claimed in claim 7 cladding, its feature exist
In step 3) described in lithium superionic conductors cladding weight less than the superionic conductors cladding cobalt acid lithium composite
The 5% of gross weight, step 4) described in calcining heat be 700～1000 DEG C.
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