CN103367741A - Negative electrode active material and preparation method thereof, as well as lithium ion battery - Google Patents
Negative electrode active material and preparation method thereof, as well as lithium ion battery Download PDFInfo
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- CN103367741A CN103367741A CN2012100819818A CN201210081981A CN103367741A CN 103367741 A CN103367741 A CN 103367741A CN 2012100819818 A CN2012100819818 A CN 2012100819818A CN 201210081981 A CN201210081981 A CN 201210081981A CN 103367741 A CN103367741 A CN 103367741A
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- active core
- shell material
- negative active
- tin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 47
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims abstract description 31
- 239000011258 core-shell material Substances 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 38
- 229910052718 tin Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 6
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052744 lithium Inorganic materials 0.000 abstract description 41
- 238000000034 method Methods 0.000 abstract description 40
- 230000008569 process Effects 0.000 abstract description 17
- 230000008859 change Effects 0.000 abstract description 7
- 229910002804 graphite Inorganic materials 0.000 abstract description 7
- 239000010439 graphite Substances 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 13
- -1 phosphate radical Chemical class 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000006182 cathode active material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
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- 239000012467 final product Substances 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 159000000002 lithium salts Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a negative electrode active material and a preparation method thereof. The negative electrode active material comprises stannous pyrophosphate, and tin and carbon which are positioned on the surface of the stannous pyrophosphate. The negative electrode active material prepared by the method can be used for obviously improving the reversible specific capacity of a battery, has high efficiency of serving as the negative electrode active material of the battery for the first time and has a stable structure, high heat stability and high cycling stability, and the tap density of the material is obviously improved. The negative electrode active material prepared by the method is in an amorphous state; the volume change is little in a lithium embedding process; the quality specific capacity can reach twice of the theory specific capacity of the existing commercial graphite. The negative electrode active material is simple, easily available, easy to prepare, low in cost and easy to apply commercially, and establishes a basis for the development of lithium ion batteries.
Description
Technical field
The present invention relates to the lithium ion battery field, more particularly, relate to a kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery.
Background technology
Lithium ion battery has the advantages such as voltage height, specific energy is large, security performance is good.At present the negative active core-shell material of commercial lithium-ion batteries mainly is graphite, and in the doff lithium process, the change in volume of graphite is little so have a preferably cycle performance.Graphite passes through LiC
6The reversible storage of compound Li
+, its Theoretical Mass specific capacity only has 372 mAh/g.Therefore, Chinese scholars all is devoted to developing of Novel anode material.Metallic tin has the advantages such as theoretical specific capacity height (specific discharge capacity is 994 mAh/g), low temperature performance excellent, fast charging and discharging performance are good, is the focus of present non-carbon negative pole material research.
But because that the volumetric expansion multiple that causes tin-based material is taken off in the embedding of lithium ion is large, structure is suffered to destroy and gradually efflorescence in charge and discharge process, has first the shortcomings such as the high and cycle performance of irreversible capacity is relatively poor, has limited its commercial application.These shortcomings for the Sn sill, modified method commonly used has metal alloy, the material structure amorphization, reduce grain graininess or synthetic tin compound as lithium ion battery negative material, tin ash for example, but every mole of tin ash consumes 8.4 mole of lithium in the embedding lithium process first, wherein has 4 mole of lithium and oxygen to form Li
2O, forming dead lithium can not deviate from, therefore irreversible capacity is high first, removal lithium embedded efficient only has 52.4% first, lithium and tin form the huge expansion (300%) of process volume generation of alloy in addition, the effect that particle is subject to ambient stress can occur particle efflorescence, come off, thereby cause the cycle performance of battery poor.Existing existing disclosing a kind ofly places porous calcium phosphate salt glass with tin oxide, reach high power capacity and low loop attenuation, synthetic a kind of unformed metal oxide materials that can store up lithium, its coulombic efficiency can reach the efficient of hydrogen bearing alloy, and the charged confining force of 100 all after dates that circulates is still near 1.To Sn
2BPO
6And Sn
2P
2O
7Electrochemical lithiation research in, the reversible capacity of the period 1 of bi-material is all greater than 500mAh/g, circulation and high rate during charging-discharging are also better, but the first efficient of these materials does not still reach desirable requirement, and the tap density of material is low.
Summary of the invention
The present invention is still lower for the first efficient that solves existing Sn base negative electrode active material, and the technical problem that the tap density of material is little provide a kind of preparation technology simple, and efficient is higher first, good cycle, the negative active core-shell material that tap density is high.
An object of the present invention is to provide a kind of negative active core-shell material, the tin and the carbon that comprise stannous pyrophosphate and be positioned at the stannous pyrophosphate surface.
Another object of the present invention provides a kind of preparation method of negative active core-shell material, and step comprises:
S1, the solution that will contain Xi Yuan mixes with the solution that contains the phosphorus source, reacts to get aaerosol solution;
S2 is mixed to get mixed system with step S1 gained aaerosol solution and carbon source;
S3, mixed system is dry, and sintering gets negative active core-shell material under protective atmosphere afterwards.
A further object of the present invention provides a kind of lithium ion battery, comprises housing, is in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Positive plate comprises positive collector and is coated in positive electrode on the positive collector; Negative plate comprises negative collector and is coated in the negative material of bearing on the collector; Wherein, negative material comprises above-mentioned negative active core-shell material.
The negative active core-shell material of the unexpected the present invention of the discovery preparation of the present inventor not only battery reversible specific capacity promotes obviously, its first efficient as the battery cathode active material is high, and Stability Analysis of Structures, and thermal stability is good, good cycling stability, the tap density of material obviously improves simultaneously.The negative active core-shell material of the present invention's preparation is amorphous state, change in volume is little in the process of embedding lithium, specific discharge capacity can reach 2 times of present business-like graphite theoretical specific capacity, infer that reason may be because the present invention adopts liquid phase method carbon source evenly can be coated on around the active particle, the reduction of recycling carbon source carbonisation becomes metallic tin with the Bivalent Tin partial reduction, used preferably the active function of simple substance tin, the first efficient of negative active core-shell material and removal lithium embedded capacity have first been improved, the unbodied stannous pyrophosphate by generating in the calcination process again, not only metallic tin is separated, slow down the bulk effect of negative active core-shell material, and stannous pyrophosphate has cycle performance and high rate during charging-discharging that high reversible capacity is become reconciled, while carbon, tin coats stannous pyrophosphate, also reduced the variation of stannous pyrophosphate volume in the process of removal lithium embedded, simultaneously the Li that generates behind the embedding lithium first of unbodied stannous pyrophosphate
2O can intercept active particle efficiently with carbon to be assembled, and further improved the cycle performance of material, and surface coated carbon can improve the electronic conductivity of material; The negative active core-shell material particle of simultaneously the present invention preparation is little, does not reunite, and tap density is high, has further improved the volume and capacity ratio of material.Simultaneously this material is simple and easy to, easily preparation, and cost is low, and easy commercial the application is for the development of lithium ion battery is laid a good foundation.
Description of drawings
Fig. 1 is the XRD(X x ray diffraction of embodiments of the invention 2 gained sample S2) figure.
Fig. 2 is the SEM(scanning electron microscopy of embodiments of the invention 1 gained sample S1) figure.
Fig. 3 (a) is the voltage-time curve figure of the battery A2 of the embodiment of the invention 2 gained sample S2 preparation.
Fig. 3 (b) is the voltage-specific capacity curve chart of the battery A2 of the embodiment of the invention 2 gained sample S2 preparation.
Fig. 4 is front 20 cycle performances and the enclosed pasture efficient of the battery A2 of the embodiment of the invention 2 gained sample S2 preparation.
Fig. 5 is the cyclic voltammetry curve of the battery A2 of the embodiment of the invention 2 gained sample S2 preparation.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of negative active core-shell material, the tin and the carbon that comprise stannous pyrophosphate and be positioned at the stannous pyrophosphate surface, the battery reversible specific capacity of its preparation promotes obviously, its first efficient as the battery cathode active material is high, and Stability Analysis of Structures, thermal stability is good, good cycling stability, and the tap density of material obviously improves simultaneously.
Preferably, carbon is coated on tin surfaces, can further intercept the reunion of active particle, the efflorescence of the negative active core-shell material that the system effect of obstruct tin is brought, the cycle performance of material further is provided, the carbon on surface can improve the electronic conductivity of material simultaneously, also can stop tin to be reunited in the process of removal lithium embedded.
Preferably, take the total amount of negative active core-shell material as benchmark, negative active core-shell material comprises the stannous pyrophosphate of 60-80wt%, the tin of 8-20wt% and the carbon of 8-20wt%.Further preferred, negative active core-shell material comprises the stannous pyrophosphate of 70-78wt%, the tin of 10-15wt% and the carbon of 10-15wt%,, thereby further optimize the tap density of first charge-discharge efficiency, charge-discharge performance and the material of material.
Preferably, the particle median particle diameter of negative active core-shell material is 0.5-10um, further optimizes the tap density of material.
The present invention provides a kind of preparation method of negative active core-shell material simultaneously, and step comprises: S1, and the solution that will contain Xi Yuan mixes with the solution that contains the phosphorus source, reacts to get aaerosol solution; Mix the present invention without limits, for example, can first Xi Yuan be configured to contain the solution of Xi Yuan, the solution that contains Xi Yuan can be the aqueous solution of Xi Yuan and water configuration, and the phosphorus source is configured to contain the solution in phosphorus source, the solution that contains the phosphorus source aqueous solution that can be the phosphorus source dispose with water, then the aqueous solution with them directly mixes, perhaps the aqueous solution with Xi Yuan adds in the aqueous solution in phosphorus source, can stir, and makes its homogeneous reaction.The present invention preferably slowly adds the solution that contains the phosphorus source in the solution that contains Xi Yuan to get aaerosol solution under stirring condition, make reaction more even, the suspended particulate uniform particle diameter of formation.Stirring the present invention be not particularly limited, and for example can be magnetic agitation, and is generally in the better situation, more complete for making reaction, continues stirring reaction a period of time after having added again, and can be 0.3-2h.The speed of slowly adding is preferably 6-50ml/min.This step preferred ambient of the present invention is that room temperature to 80 is ℃ better, namely mixes among the step S1, the temperature of reaction can be room temperature to 80 ℃, and heating can be adopted heating water bath.
S2 is mixed to get mixed system with step S1 gained aaerosol solution and carbon source; Mix the present invention without limits, for example, can directly add carbon source to aaerosol solution, also can first carbon source be configured to the aqueous solution of carbon source, aaerosol solution directly be mixed with the carbon source aqueous solution, or aaerosol solution is added in the carbon source aqueous solution, can stir it is mixed, under the better condition, the carbon source aqueous solution is added in the aaerosol solution under the condition that stirs, after continue again to stir 0.5-2 hour.This step preferred ambient of the present invention is that room temperature to 80 is ℃ better, and the temperature of namely mixing among the step S2 can be room temperature to 80 ℃, and heating can be adopted heating water bath.
S3, mixed system is dry, and sintering gets negative active core-shell material under protective atmosphere afterwards.Protective atmosphere can be inert atmosphere, and atmosphere such as helium, neon, argon, krypton, xenon perhaps is nitrogen atmosphere.For example the material after the vacuumize can be changed in the tube furnace that is connected with argon gas stream, be lower than 700 ℃ of temperature insulation a period of times, cooling obtains product naturally.The temperature that the temperature of preferred sintering namely is incubated is 500-700 ℃, and the time that the time of sintering namely is incubated is 1-10 h, and the heating rate of sintering is 2-10 ℃/min.Sintering can be one-stage sintering, also can be in sintering furnace mobile multistage sintering etc., the present invention is without limits.When carbon source is organic polymer, during sintering, the organic polymer of precipitation surface can resolve into carbon coating layer, Bivalent Tin partial reduction during the reduction of carbonisation will precipitate simultaneously becomes metallic tin, precipitation generates unbodied stannous pyrophosphate by calcination process again simultaneously, thereby forms the negative active core-shell material of unique texture.
Comprise also before the preferred steps S3 drying of the present invention that the pH value of regulating mixed system for 2-8, stirs to get sol system, it is little that sol system can access particle diameter, and the granular precursor of narrowly distributing is further optimized the coating of carbon source, coats more homogeneous.The pH value of regulating mixed system can adopt and well known to a person skilled in the art various alkaline solutions, the general preferred pH value of selecting is the alkaline solution of 8-14, can be the ammoniacal liquor of 15%-30% for concentration for example, preferably, the pH value of regulating mixed system is 2-8 for 2-8 is included in mixed system interpolation ammoniacal liquor adjusting pH value, can obtain better sol system, optimizes grain diameter, ammonia is volatile simultaneously, adds ammoniacal liquor and can not introduce foreign ion.Be generally and make reaction evenly, generally under stirring condition, add adjustment pH value, also can stir a period of time again in the better situation, make and react completely, the preferred time of stirring is 30min-2h, the temperature that stirs can be room temperature to 80 ℃, be in heated condition such as system, in the time of can being stirred to deionized water and being evaporated to half left and right sides, it is dry directly to put into drying box, also can adopt react completely after with precipitate and separate, rear washing, drying, wherein, precipitate and separate can adopt the mode of existing various precipitate and separate, such as suction filtration, centrifugation, the evaporate to dryness aqueous solution etc.Washing general employing ethanol and deionized water supersound washing, the number of times of washing can carry out according to actual conditions, for example can wash three times, and it is mainly removes residual foreign ion.Drying can adopt and well known to a person skilled in the art various drying modes, and 50-100 ℃ of drying for example, this step preferred ambient of the present invention are that room temperature to 80 is ℃ better, and heating can be adopted heating water bath.
Wherein, Xi Yuan is generally water-soluble stanniferous ionic species, the material of the tin ion that in water, can dissociate out that can be water-soluble, the present invention can adopt and well known to a person skilled in the art this type of material, the preferred Xi Yuan of the present invention is pink salt, can for well known to a person skilled in the art various pink salts, for example can be selected from butter of tin, stannous chloride, stannous sulfate or the phosphoric acid stannous chloride one or more; The present invention of phosphorus source also without limits, be preferably water-soluble phosphorous acid group or phosphoric acid hydrogen radical ion material, the material of in water, can dissociate out phosphate radical or phosphoric acid hydrogen radical ion that can be water-soluble, the preferred phosphorus of the present invention source is phosphoric acid, dibasic alkaliine, dihydric phosphate, for example can be selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate or the phosphoric acid one or more; Carbon source the present invention only needs to form carbon coated in precipitation surface and gets final product without limits, is preferably organic polymer, coat more even, not only itself can resolve into carbon coating layer when sintering, and the reduction of carbonisation is stronger, the Bivalent Tin partial reduction in the precipitation can be become metallic tin.For example carbon source can be selected from one or both in glucose, fructose, citric acid, sucrose or the cellulose.
When the solution that contains Xi Yuan mixed with the solution that contains the phosphorus source, preferred, the ratio of the mole of the P in the Sn in the tin source and the phosphorus source (being quality or mole) was Sn:P=1:0.5-1.5; When aaerosol solution mixed with carbon source, the amount of the carbon source of preferably selecting was that the ratio of the C mole (being quality or mole) of Sn in the tin source and carbon source is Sn:C=1:1-30.Generally Xi Yuan, phosphorus source, carbon source are configured to the aqueous solution, the general dissolving of concentration gets final product.
The present invention also discloses a kind of lithium ion battery, comprise housing, be in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Positive plate comprises positive collector and is coated in positive electrode on the positive collector; Negative plate comprises negative collector and is coated in the negative material of bearing on the collector; Wherein, negative material comprises above-mentioned negative active core-shell material.Negative material also comprises binding agent, conductive agent etc. usually; also can contain additive etc.; the preparation method of negative plate adopts and well known to a person skilled in the art the whole bag of tricks; for example; above-mentioned negative active core-shell material and binding agent, conductive agent and additive etc. are dissolved in according to a certain percentage are mixed into the negative pole slurries in the solvent, apply the negative pole slurries at the wide cut negative electrode collector again, then dry; roll-in is also cut, and obtains negative plate.Wherein, binding agent is this area various materials commonly used, and for example described binding agent is selected from one or more in sodium carboxymethylcellulose, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, ethylene/propylene/diene hydrocarbon terpolymer, sulfonated EPDM, styrene/butadiene rubbers and the fluorubber.Preferred binding agent is the compound binding agent of styrene/butadiene rubbers and sodium carboxymethylcellulose.The content of various materials is not too large restriction also, can adopt various relation with contents of the prior art, and for example negative active core-shell material, weight of binder are preferably 10-35:1 than for 5-50:1.Wherein, when adopting compound binding agent, the weight ratio of styrene/butadiene rubbers and sodium carboxymethylcellulose is 0.5-4:1.Condition dry and roll-in is known in those skilled in the art, and for example the temperature of dry negative plate is generally 60-120 ℃, and preferred 80-110 ℃, be 0.5-5 hour drying time.
The pole piece structure of battery provided by the present invention is this area pole piece structure commonly used, and in general, pole piece can adopt the mode of coiling or stacked positive plate, barrier film and negative plate to make, and coiling or stacked mode are that those skilled in the art are in common knowledge.
The present invention has no particular limits positive electrode, and is the same with prior art, and positive electrode generally includes positive active material, binding agent and conductive agent.Positive active material can adopt up to now can commercial all positive electrodes, such as LiFePO
4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F, LiFeO
2Deng, perhaps ternary system Li
1+xL
1-y-zM
yN
zO2, wherein-0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0, L, M, N are at least a in Co, Mn, Ni, Al, Mg, Ga and the 3d transiting group metal elements.Binding agent can adopt any binding agent known in the field, for example can adopt in polyvinylidene fluoride, polytetrafluoroethylene or the butadiene-styrene rubber one or more.The content of binding agent is the 0.1-15wt% of described positive electrode, is preferably 1-7wt%.Conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.The content of described conductive agent is the 0.1-20wt% of described positive electrode, is preferably 2-10wt%.The preparation method of positive plate can adopt this area the whole bag of tricks commonly used, for example with solvent positive active material, binding agent and conductive agent are prepared into the positive electrode slurries, the addition of solvent is known in those skilled in the art, and the viscosity that can be coated with according to the slurry of anodal slurries to be prepared and the requirement of operability are adjusted flexibly.Then prepared positive electrode slurries slurry is coated in dry compressing tablet on the positive electrode collector, cut-parts obtain positive plate again.The temperature of described drying is generally 120 ℃, and be generally 5 hours drying time.The used solvent of anodal slurries can be various solvent of the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, it is the 40-90 % by weight that the consumption of solvent makes the content of positive active material in the slurries, is preferably the 50-85 % by weight.
The barrier film of battery of the present invention has electrical insulation capability and liquid retainability energy.Barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
The electrolyte of battery of the present invention is nonaqueous electrolytic solution.Nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol/L, is preferably the 0.8-1.2 mol/L.
The preparation method of battery of the present invention is well known for the person skilled in the art, and in general, the preparation method of this battery comprises pole piece is inserted in the battery case that encapsulation obtains battery.Wherein, encapsulation comprises puts into battery container with Battery Pole Core, and welded cover plate and battery container inject electrolyte, battery is changed into and seals in battery container, change into, the technology such as sealing adopts and well known to a person skilled in the art various technology, the present invention is not particularly limited.
The present invention such as positive electrode collector of the present invention, negative electrode collector are not particularly limited, can adopt well known to a person skilled in the art various positive electrode collectors,, negative electrode collector, again do not do and give unnecessary details.
Below in conjunction with specific embodiment the present invention is further described.
The stannous chloride with 2 crystallizations water of 4.51g is dissolved in the deionized water of 40ml, form solution A, the diammonium hydrogen phosphate of 1.85g is dissolved in the deionized water of 40ml and forms solution B, the glucose of 8g is dissolved in the deionized water of 40ml and forms solution C, then under the condition that stirs, solution B dropwise is added drop-wise to formation white suspension solution in the A solution with 6ml/min, after being added dropwise to complete, continue again stirring reaction 1h, after C solution is added in the above-mentioned white suspension solution again, continue to stir 30min, above-mentioned reaction is all carried out under 60 ℃ water bath condition, adopt at last 30wt% ammoniacal liquor regulate the pH value to 4.2 of above-mentioned aaerosol solution; Stir and treated that deionized water was evaporated to a half and stops to stir in 4 hours, the baking oven of product being put into 60 ℃ carries out drying and processing.Change over to again after the drying in the tube furnace that is connected with argon gas, rise to 650 ℃ of insulation 4h with the programming rate of 5 ℃/min, naturally lower the temperature, obtain sample S1.
According to the stannous pyrophosphate that contains 72wt% among the sample S1 that obtains making that converts after elemental analyser, the carbon and sulfur analytical instrument test, the tin of 13wt%, the carbon of 15wt%.
The particle median particle diameter that adopts particle size analyzer to record sample S1 is about 2um.
Embodiment 2
The stannous sulfate of 4.3g is dissolved in the deionized water of 30ml and forms solution A, the diammonium hydrogen phosphate of 2.3g is dissolved in the deionized water of 60ml and forms solution B, the citric acid of 6g is dissolved in the deionized water of 30ml and forms solution C; Under the condition that stirs, solution B 10ml/min dropwise is added drop-wise to and forms white suspension solution in the A solution, after being added dropwise to complete, continue again stirring reaction 30min, again C solution is added in the aaerosol solution of white, continue to stir the above-mentioned reaction of 30min and all under 50 ℃ water bath condition, carry out, then adopt the ammoniacal liquor of 30wt% to regulate pH value to 6.8; Stir and treated that deionized water was evaporated to a half and stops to stir in 2 hours, the vacuum drying chamber of product being put into 100 ℃ carries out drying and processing.Change over to again after the drying in the tube furnace that is connected with nitrogen, rise to 600 ℃ of insulation 5h with the programming rate of 3 ℃/min, naturally lower the temperature, obtain sample S2.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 75wt% among the sample S2 that makes, the tin of 12.2wt%, the carbon of 12.8wt%.The particle median particle diameter of sample S2 is about 1.8 um.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, different is with the stannous sulfate of 4.3g is dissolved in the deionized water of 50ml and forms solution A, the diammonium hydrogen phosphate of 2.3g is dissolved in the deionized water of 50ml and forms solution B, the citric acid of 6g is dissolved in forms solution C in the deionized water of 30ml and make sample S3.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 74.5wt% among the sample S3 that makes, the tin of 11.6wt%, the carbon of 13.9 wt%.The particle median particle diameter of sample S3 is about 2.6um.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, different is with the stannous sulfate of 4.3g is dissolved in the deionized water of 30ml and forms solution A, the diammonium hydrogen phosphate of 2.3g is dissolved in the deionized water of 50ml and forms solution B, the citric acid of 5g is dissolved in forms solution C in the deionized water of 100ml and make sample S4.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 75wt% among the sample S4 that makes, the tin of 13.4wt%, the carbon of 11.6wt%.The particle median particle diameter of sample S4 is about 2.5um.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, different is with the stannous sulfate of 4.3g is dissolved in the deionized water of 30ml and forms solution A, the diammonium hydrogen phosphate of 2.3g is dissolved in the deionized water of 50ml and forms solution B, the citric acid of 3g is dissolved in forms solution C in the deionized water of 20ml and make sample S5.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 80wt% among the sample S5 that makes, the tin of 9wt%, the carbon of 11wt%.The particle median particle diameter of sample S5 is about 3um.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, the temperature of different is sintering is 520 ℃, makes sample S6.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 73.5wt% among the sample S6 that makes, the tin of 10.5wt%, the carbon of 16wt%.The particle median particle diameter of sample S6 is about 1.9um.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, the temperature of different is sintering is 680 ℃, makes sample S7.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 71.5wt% among the sample S7 that makes, the tin of 13.8wt%, the carbon of 14.7wt%.The particle median particle diameter of sample S7 is about 1.8um.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, the temperature of different is sintering is 730 ℃, makes sample S8.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 70.6wt% among the sample S8 that makes, the tin of 16wt%, the carbon of 13.4wt%.The particle median particle diameter of sample S8 is about 1.5um.
Embodiment 9
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, different is do not add 30wt% ammoniacal liquor, namely do not regulate the pH value of aaerosol solution, make sample S9.
Adopt the method identical with embodiment 1 to record the stannous pyrophosphate that contains 77wt% among the sample S9 that makes, the tin of 10.7wt%, the carbon of 12.3wt%.The particle median particle diameter of sample S9 is 2.9um.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare negative active core-shell material, different is not add B solution, directly C solution is added in the A solution, prepares the tin base cathode active material D1 of carbon coating.
Adopt the method identical with embodiment 1 to record the tin that contains 80.5wt% among the sample D1 that makes, the carbon of 18.5wt%, the particle median particle diameter of sample D1 is about 0.5um.
Comparative Examples 2
With 3 g SnF
2With 8.8 g H
3PO
4(85%) join successively in the 100 mL deionized waters, A solution dropwise is added drop-wise in the B solution with 2 ml/min clock rate, behind magnetic agitation 0.5 h, be transferred in the hydrothermal reaction kettle 90 ℃ of insulations 20 hours, then centrifugation goes out white precipitate.Use respectively ethanol and deionized water supersound washing precipitated product twice, precipitated product was obtained final products in 5 hours 400 ℃ of heat treatments.Vacuumize obtains stannous pyrophosphate sample D2.
The particle median particle diameter that adopts the method identical with embodiment 1 to record sample D2 is about 0.4um.
Performance test
1, X-ray diffraction analysis
Adopt Rigaku D-MAX/2550 type X-ray diffractometer that embodiment 2 gained sample S2 are carried out X-ray diffraction analysis and get Fig. 1, there is not obvious diffraction maximum in the XRD collection of illustrative plates of sample, the product that shows acquisition is amorphous amorphous state, show to have generated unbodied negative active core-shell material that this amorphous state product can not produce obvious crystal boundary and cracked phenomenon as crystal grain in the charge and discharge cycles process.The highest peak of the corresponding stannous pyrophosphate of amorphous broad peak in 2 θ=25 °.
2, Electronic Speculum
Adopt Japanese JSM 6360LV type ESEM that embodiment 1 gained sample S1 is carried out electron-microscope scanning and get Fig. 2, as can be seen from the figure, particle is structure in the form of sheets, and size is between 0.5-2 μ m, mutually with stacked in layers, this stack manner can effectively improve the tap density of material between the particle.
3, elementary analysis
Adopting Japanese JY 238 ULTRACE ICP-AES-ICP-AESs that embodiment 1 gained sample S1 is carried out constituent content analysis must table 1, and can draw molecular composition from table 1 is Sn
1.56P
1.1O
4, remaining material is amorphous carbon.
4, tap density
Employing graduated cylinder method must table 2 to the tap density of embodiment 1-9 and Comparative Examples 1-2 gained sample S1-S9 and D1-D2 test material.
5, chemical property
Prepare as follows battery:
In mass ratio with the negative active core-shell material sample S1-S9 of embodiment 1-9, Comparative Examples 1,2 negative active core-shell material sample D1, D2, according to negative active core-shell material: the ratio of SBR:CMC=100:6:4 mixes rear compressing tablet, and 120 ℃ of vacuumize 24h obtain the work pole piece; Take metal lithium sheet as to electrode, the celgard2400 polypropylene porous film is barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample A1-A9, battery sample DA1, DA2.
5.1 charging and discharging capacity
It is work electrode embedding lithium that battery sample A1-A9, DA1, DA2 are set to discharge condition, three sections constant-current discharges: constant current section one, 120mAh/g, cut-ff voltage 5mV; Constant current section two, 60mAh/g, cut-ff voltage 5mV; Constant current section three, 30mAh/g, cut-ff voltage 5mV; Charging process adopts constant current charge: 120mAh/g, cut-ff voltage is 2.5V, out of service, calculate first discharge specific capacity, the voltage-time curve figure of A2 battery shown in Fig. 3 (a), the voltage of A2 battery-specific capacity curve chart is shown in Fig. 3 (b).
The quality of first embedding lithium specific capacity (mAh/g)=first embedding lithium capacity/active material.
After the embedding lithium finished first, to be set to charged state be that work electrode takes off lithium to battery again, and charging current is 120mAh/g, and charge cutoff voltage is 2.5V, and charging finishes, and calculates the initial charge specific capacity.
Take off first the quality that lithium specific capacity (mAh/g)=is first taken off lithium capacity/active material.
The embedding lithium specific capacity of efficient=take off first lithium specific capacity/first first.
From Fig. 3 (a), can find out, negative material of the present invention does not have obvious embedding lithium platform about 0.8V, illustrate that this material does not have obvious irreversible reaction near 0.8V, illustrate that this material has high first charge-discharge efficiency, the embedding lithium platform about 0.2V then corresponding lithium and metallic tin forms the process of alloy; Near other then corresponding the lithium process of from alloy, deviating from of lithium platform of taking off 0.5V.
Can find out that from Fig. 3 (b) the first embedding lithium specific capacity of material is 832.52 mAh/g, taking off first the lithium specific capacity is 760.32 mAh/g, and efficient is 91.33% first, and after once circulating, the first efficient of material is brought up to more than 96%.
5.2 cycle performance:
Constant current with 5mA carries out constant current charge to battery sample A1-A9, battery sample DA1, DA2, charging is by voltage 1.5V, equally with the constant current of 5mA to the battery constant-current discharge, discharge cut-off voltage is 0.010V, shelves 10 minutes, repeats above step, make continuous charge-discharge test, obtain the battery capacity after battery circulates for 100 times, calculate the discharge capacitance of 100 rear batteries of circulation, test result is as shown in table 1.
Take off and take off lithium capacity/take off first lithium capacity * 100% after the circulation of lithium capability retention=100 time.
Fig. 4 is front 20 cycle performances and the enclosed pasture efficient of battery sample A2, and charging current is 120mAh/g, and charge cutoff voltage is 2.5V, three sections constant-current discharges: constant current section one, 120mAh/g, cut-ff voltage 5mV; Constant current section two, 60mAh/g, cut-ff voltage 5mV; Constant current section three, 30mAh/g, cut-ff voltage 5mV; Charging process adopts constant current charge: 120mAh/g, and cut-ff voltage is 2.5V.After material circulated through 5 times, efficiency for charge-discharge reached more than 98%, and through 20 circulations, efficient reaches 99%, and material its specific discharge capacities after 20 circulations still remain on more than the 500mAh/g.
Fig. 5 be battery sample A2 cyclic voltammetry curve, sweep speed is 0.5mV/s.In the cyclic process, a reduction peak is arranged about 1.4V first, corresponding the reduction peak of stannous pyrophosphate.
Table 1
| Element | Tester | The result | Unit |
| Tin | ICP | 48.70 | % |
| Phosphorus | ICP | 8.99 | % |
| Oxygen | N/O | 16.87 | % |
Table 2
| Battery sample | The content of stannous pyrophosphate | The content of tin | The content of carbon | Particle diameter (um) | Tap density (g/cm 3) |
| S1 | 72 | 13 | 15 | 2.0 | 1.5 |
| S2 | 75 | 12.2 | 12.8 | 1.8 | 1.4 |
| S3 | 74.5 | 11.6 | 13.9 | 2.6 | 1.3 |
| S4 | 75 | 13.4 | 11.6 | 2.5 | 1.3 |
| |
80 | 9 | 11 | 3 | 1.1 |
| S6 | 73.5 | 10.5 | 16 | 1.9 | 1.3 |
| S7 | 71.5 | 13.8 | 14.7 | 1.8 | 1.6 |
| S8 | 70.6 | 16 | 13.4 | 1.5 | 2.0 |
| S9 | 77 | 10.7 | 12.3 | 2.9 | 1.1 |
| |
0 | 80.5 | 18.5 | 0.5 | 0.9 |
| D2 | 98.3 | 0 | 0 | 0.4 | 0.8 |
Table 3
| Battery sample | Embedding lithium specific capacity (mAh/g) first | Take off first lithium specific capacity (mAh/g) | Coulombic efficiency (%) first circulates | Lithium capability retention (%) is taken off in 100 circulations |
| A1 | 825.36 | 748.11 | 90.64 | 58.3 |
| A2 | 832.52 | 760.32 | 91.33 | 59.2 |
| A3 | 850.25 | 768.29 | 90.36 | 58.5 |
| A4 | 830.72 | 755.96 | 90.00 | 58.7 |
| A5 | 750.32 | 615.26 | 82.00 | 42.1 |
| A6 | 840.34 | 750.08 | 89.26 | 53.8 |
| A7 | 883.72 | 805.33 | 91.12 | 56.4 |
| A8 | 891.28 | 804.64 | 90.28 | 53.5 |
| A9 | 810.46 | 651.04 | 80.33 | 40.2 |
| DA1 | 1100 | 631 | 57.36 | 36.45 |
| DA2 | 760.82 | 408.40 | 53.68 | 32.35 |
The negative active core-shell material of the present invention's preparation not only battery reversible specific capacity promotes obviously, and its first efficient as the battery cathode active material is high, and Stability Analysis of Structures, and thermal stability is good, good cycling stability, and the tap density of material obviously improves simultaneously.The negative active core-shell material of the present invention's preparation is amorphous state, change in volume is little in the process of embedding lithium, specific discharge capacity can reach 2 times of present business-like graphite theoretical specific capacity, can reach 91% with the first efficient of the battery of its preparation, and the tap density of material is high.Simultaneously this material is simple and easy to, easily preparation, and cost is low, and easy commercial the application is for the development of lithium ion battery is laid a good foundation.
Those skilled in the art know easily; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (19)
1. a negative active core-shell material is characterized in that, the tin and the carbon that comprise stannous pyrophosphate and be positioned at the stannous pyrophosphate surface.
2. negative active core-shell material according to claim 1 is characterized in that, described carbon is coated on tin surfaces.
3. negative active core-shell material according to claim 1 is characterized in that, take the total amount of negative active core-shell material as benchmark, described negative active core-shell material comprises the stannous pyrophosphate of 60-80wt%, the tin of 8-20wt% and the carbon of 8-20wt%.
4. negative active core-shell material according to claim 3 is characterized in that, take the total amount of negative active core-shell material as benchmark, described negative active core-shell material comprises the stannous pyrophosphate of 70-78wt%, the tin of 10-15wt% and the carbon of 10-15wt%.
5. negative active core-shell material according to claim 1 is characterized in that, the particle median particle diameter of described negative active core-shell material is 0.5-10um.
6. the preparation method of a negative active core-shell material as claimed in claim 1 is characterized in that, step comprises:
S1, the solution that will contain Xi Yuan mixes with the solution that contains the phosphorus source, reacts to get aaerosol solution;
S2 is mixed to get mixed system with step S1 gained aaerosol solution and carbon source;
S3, mixed system is dry, and sintering gets negative active core-shell material under protective atmosphere afterwards.
7. preparation method according to claim 6 is characterized in that, comprises also before the described step S3 drying that the pH value of regulating mixed system for 2-8, stirs to get sol system.
8. preparation method according to claim 7 is characterized in that, the pH value of described adjusting mixed system is 2-8 for 2-8 is included in mixed system interpolation ammoniacal liquor adjusting pH value.
9. preparation method according to claim 7 is characterized in that, the time of described stirring is 30min-2h, and the temperature of stirring is room temperature to 80 ℃.
10. preparation method according to claim 6 is characterized in that, described step S1 comprises that the solution that will contain the phosphorus source slowly adds in the solution that contains Xi Yuan to get aaerosol solution under stirring condition.
11. preparation method according to claim 6 is characterized in that, the temperature of sintering is 500-700 ℃ among the described step S3.
12. preparation method according to claim 6 is characterized in that, the time of sintering is 1-10 h among the described step S3.
13. preparation method according to claim 6 is characterized in that, the heating rate of sintering is 2-10 ℃/min among the described step S3.
14. preparation method according to claim 6 is characterized in that, temperature dry among the described step S3 is 50-100 ℃.
15. preparation method according to claim 6 is characterized in that, the temperature of mixing among the described step S1, mixing among the temperature of reaction or the step S2 is room temperature to 80 ℃.
16. preparation method according to claim 6 is characterized in that, described Xi Yuan is selected from one or more in butter of tin, stannous chloride, stannous sulfate or the phosphoric acid stannous chloride;
Described phosphorus source is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate or the phosphoric acid;
Described carbon source is selected from one or both in glucose, fructose, citric acid, sucrose or the cellulose.
17. preparation method according to claim 6 is characterized in that, the ratio of the mole of the P in the Sn in the described tin source and the phosphorus source is Sn:P=1:0.5-1.5; Sn in the described tin source is Sn:C=1:1-30 with the ratio of the C mole of carbon source.
18. preparation method according to claim 6 is characterized in that, described protective atmosphere is helium atmosphere, neon atmosphere, argon gas atmosphere, Krypton atmosphere, xenon atmosphere or nitrogen atmosphere.
19. a lithium ion battery comprises housing, is in electrolyte between the pole piece at the cover plate of the pole piece of enclosure interior, seal casinghousing and in enclosure interior; Described pole piece comprises positive and negative plate and the barrier film between positive/negative plate; Described positive plate comprises positive collector and is coated in positive electrode on the positive collector; Described negative plate comprises negative collector and is coated in the negative material of bearing on the collector; It is characterized in that described negative material comprises each described negative active core-shell material of claim 1-5.
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| CN109494348A (en) * | 2018-10-17 | 2019-03-19 | 宁德时代新能源科技股份有限公司 | Negative pole piece and secondary battery |
| CN110931767A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof |
| CN111747393A (en) * | 2020-07-13 | 2020-10-09 | 武汉科技大学 | Preparation method of porous pyrophosphate and sodium ion battery |
| CN113036101A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Carbon-coated pyrophosphate and preparation method and application thereof |
| CN114597406A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-coated tin pyrophosphate |
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| JP2014116273A (en) * | 2012-12-12 | 2014-06-26 | Nippon Telegr & Teleph Corp <Ntt> | Sodium secondary battery |
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| CN110931767A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof |
| CN110931767B (en) * | 2019-12-19 | 2021-06-11 | 哈工大泰州创新科技研究院有限公司 | SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof |
| CN111747393A (en) * | 2020-07-13 | 2020-10-09 | 武汉科技大学 | Preparation method of porous pyrophosphate and sodium ion battery |
| CN114597406A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-coated tin pyrophosphate |
| CN113036101A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Carbon-coated pyrophosphate and preparation method and application thereof |
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