CN113921780A - A kind of multi-shell-coated composite hollow structure material and its preparation method and application - Google Patents
A kind of multi-shell-coated composite hollow structure material and its preparation method and application Download PDFInfo
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- CN113921780A CN113921780A CN202111061142.5A CN202111061142A CN113921780A CN 113921780 A CN113921780 A CN 113921780A CN 202111061142 A CN202111061142 A CN 202111061142A CN 113921780 A CN113921780 A CN 113921780A
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- Prior art keywords
- oxide
- dioxide
- coated
- hollow
- nanoparticles
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 90
- 239000000463 material Substances 0.000 claims abstract description 75
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 110
- 239000004408 titanium dioxide Substances 0.000 claims description 55
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 41
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000967 suction filtration Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 20
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 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 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 229940011182 cobalt acetate Drugs 0.000 claims description 13
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229940119177 germanium dioxide Drugs 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011796 hollow space material Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 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
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 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
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims 4
- 229910052788 barium Inorganic materials 0.000 claims 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 239000001119 stannous chloride Substances 0.000 claims 1
- 235000011150 stannous chloride Nutrition 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011257 shell material Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000005543 nano-size silicon particle Substances 0.000 description 26
- 238000001816 cooling Methods 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 150000003376 silicon Chemical class 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 description 2
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 2
- 229920002527 Glycogen Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention relates to a multi-shell coated composite hollow structure material and a preparation method and application thereof, and the preparation method comprises the following steps: 1) dispersing the coated body into an aqueous solution containing a surfactant to obtain a surfactant-modified coated body; 2) dispersing the modified hollow spheres and/or nanoparticles obtained in the step 1) into a carbon source aqueous solution for heating reaction to obtain a carbon-coated composite material of a plurality of hollow spheres and/or nanoparticles; 3) dispersing the carbon-coated hollow spheres and/or nanoparticles obtained in the step 2) in a metal salt solution to obtain a solid precursor of the carbon-coated composite material; 4) roasting the solid precursor of the carbon-coated composite material obtained in the step 3) to obtain the multi-shell coated composite hollow structure material. The material can maintain specific capacity of 1372.4mAh/g, the capacity is kept to 92.3% of the initial capacity after circulating for 700 circles, and the stability performance of the material is far superior to that of a directly mixed material of the same components.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a multi-shell coated composite hollow structure material and a preparation method and application thereof.
Background
In recent years, with the increasing consumption of fossil energy and the problem of environmental pollution caused during development and use, development of new energy which is cheap, efficient and environment-friendly is urgently needed. Solar energy, wind energy, water energy and the like are renewable secondary energy sources and are environment-friendly. These energy sources can directly generate electricity, and in practical application, the problems of time difference and region difference can be encountered. Therefore, it is necessary to store these energy sources in the form of chemical energy and to convert the chemical energy into electric energy until the application. Electrochemical energy storage secondary battery systems are capable of balancing the relationship between energy conversion and storage. The lithium ion battery, which is the most widely used secondary battery at present, has the advantages of high energy density, high open circuit voltage, long cycle life, small self-discharge, no memory effect and the like. The energy storage is almost all lithium ion batteries no matter the mobile phones and computers used at ordinary times or new energy vehicles and electric vehicles on the road. And the energy storage system is a key component of the next generation smart grid. Therefore, high-performance lithium secondary batteries for storing alternative energy sources such as solar energy, hydroelectric power, wind power, etc. are not developed in limited quantities in the future.
The lithium ion energy density is improved, so that electronic products carried in daily life are light and small; the self weight of the automobile can be reduced, and more space in the automobile can be provided. Electrode materials have been the focus of research in lithium ion batteries as an important component in battery compositions. Graphite is a representative of the current commercial lithium ion battery cathode material, the theoretical lithium storage capacity of the graphite is only 372mAh/g, and the demand of human beings on high energy density batteries cannot be met, so that the development of a cathode material with high capacity is one of the current development targets. And metal oxides, simple substance silicon and the like which have different lithium storage mechanisms from graphite intercalation are taken as new cathode materials, and the lithium storage mechanism of the cathode materials is shown as oxidation-reduction reaction or alloying reaction with lithium ions in the charging and discharging processes. Although these materials have theoretical specific capacities far exceeding that of graphite negative electrodes (metal oxide: 600-1300mAh/g and Si:4200mAh/g), there is also a drastic volume change during charge and discharge. This change in volume subjects it to great mechanical stresses during the cycle and to gradual pulverization and collapse, losing the connection between the active material and the collector; on the other hand, the continuous breakage and generation of the SEI film by volume expansion and contraction exacerbates the loss of the electrolyte and ultimately leads to the failure of the battery.
At present, the modification work aiming at the redox reaction or alloying electrode material is mainly embodied in two aspects, namely, the mechanical stress of the electrode material in the volume expansion process is released by nanocrystallization of the electrode material, and the pulverization of the electrode material in the circulation process is further prevented; and secondly, the structure is designed to buffer the volume expansion in the charge-discharge process and stabilize the SEI film, so that ideal electrochemical performance is obtained. Around these two aspects, researchers have conducted many material design works to effectively improve the performance of the redox reaction or alloying electrode material, but still have the problems of short cycle life, poor rate capability and low energy density, and still cannot meet the actual commercial application requirements at present.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a multi-shell coated composite hollow structure material and a preparation method and application thereof. According to the invention, by coating a plurality of hollow spheres and/or nanoparticles in the carbon, the shell can form different metal oxides, and finally the composite material with a hollow structure containing a plurality of hollow spheres and/or nanoparticles is formed. On the basis of the method, different hollow spheres and/or nanoparticles can be mixed together to form a heterogeneous core inside. The hollow structure can buffer the volume expansion in the lithiation/delithiation process of different substances inside and outside, and the shell layer forms stable SEI. The energy density and the cycling stability of the material are greatly improved by virtue of the hollow structure and the internally loaded multiple cores.
The invention provides a negative electrode material for a lithium ion battery and a preparation method thereof. According to the invention, a plurality of hollow spheres and/or nano particles are coated with carbon, and metal ions are solidified and then calcined in an oxygen-containing atmosphere to obtain the hollow composite structure material with the multi-shell-coated multi-core structure, and the material shows excellent electrochemical performance in the application aspect of the lithium battery negative electrode by virtue of the unique structural advantages of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a multi-shell coated composite hollow structure material, namely a preparation method of a material for encapsulating a plurality of hollow spheres and/or nanoparticles in a hollow structure, which comprises the following steps:
1) adding the coated body into a surfactant solution to obtain a suspension, performing ultrasonic dispersion, stirring, centrifuging, and washing to obtain a surfactant-modified coated body; wherein the coated body comprises hollow spheres and/or nanoparticles;
2) dispersing the surfactant modified hollow spheres and/or nanoparticles obtained in the step 1) into a carbon source water solution for heating reaction, filtering, washing and drying to obtain a carbon-coated composite material with a plurality of hollow spheres and/or nanoparticles;
3) dispersing the carbon-coated hollow spheres and/or nanoparticles obtained in the step 2) in a metal salt solution to obtain a suspension, stirring, keeping the temperature, performing adsorption, performing suction filtration, and drying to obtain a solid precursor of the carbon-coated hollow spheres and/or nanoparticles composite material;
4) roasting the solid precursor of the carbon-coated multiple hollow spheres and/or nano-particle composite material obtained in the step 3) to obtain a multi-shell-coated composite hollow structure material;
in the method, modification of the surfactant, the proportion of hydrothermal carbonized materials, hydrothermal temperature and hydrothermal time are main factors for synthesizing and regulating and controlling the micro-morphology of the material. The surfactant modifies the hollow sphere and/or the nanoparticle, so that the surface of the hollow sphere and/or the nanoparticle is uniformly modified with the surfactant, and the hollow sphere and/or the nanoparticle can stably exist in a solution. After finishing the surface modification of the hollow sphere and/or the nano particle, selecting proper hydrothermal carbonization temperature and hydrothermal time are also very important parameters. As the carbonization temperature is increased, glycogen is hydrolyzed and polymerized on the surface of the hollow sphere and/or the nanoparticle which are modified by the surfactant, carbon continuously grows on the surface of the hollow sphere and/or the nanoparticle in the process of reaching the proper temperature and carrying out heat preservation, and the thickness of the coated carbon layer is increased along with the prolonging of the heat preservation process. The proportion of the carbon source, the hydrothermal temperature and the hydrothermal time in the carbonization process play a very important role in the morphology of the final material. The carbon source is too high relative to the hollow spheres and/or the nano particles, so that the homogeneous nucleation ratio is easily increased, and the coated carbon layer is very thin when the carbon source is too low; the hydrothermal temperature is too low to reach the polymerization temperature of the carbon source, and the surfactant on the surfaces of the hollow spheres and/or the nano particles can be damaged by the excessively high hydrothermal temperature; the carbon layer is very small in thickness easily caused by too short hydrothermal time, and the generated carbons are mutually adhered caused by too long hydrothermal time; the above ultimately changes the morphology to affect the properties of the material.
In addition, besides the hollow spheres and/or nanoparticles of the same kind are coated inside, hollow spheres and/or nanoparticles of different kinds can be mixed to form a hollow composite structure with a heterogeneous core inside and a multi-shell layer outside.
The plurality of hollow spheres and/or nanoparticles mentioned in the present invention is preferably, but not limited to, two or more hollow spheres and/or nanoparticles.
The hollow spheres of the present invention are well known in the art.
According to the invention, the surface of the hollow sphere and/or the nanoparticle is modified by the surfactant solution in the step 1), and compared with the hollow sphere and/or the nanoparticle which are not modified by the surfactant, the carbon source is easy to polymerize and grow on the surface of the modified hollow sphere and/or nanoparticle to form a carbon layer in the hydrothermal process.
The hollow spheres and/or nanoparticles modified by the surfactant in the step 2) are dispersed in a carbon source water solution for heating reaction to prepare a composite structure of a plurality of carbon-coated hollow spheres and/or nanoparticles, the prepared plurality of carbon-coated hollow spheres and/or nanoparticles have uniform particle size and controllable carbon layer thickness, and simultaneously the surface of the prepared plurality of carbon-coated hollow spheres and/or nanoparticles contains a large number of active functional groups, so that the composite structure has excellent hydrophilicity and surface reaction activity, is more beneficial to adsorption of metal ions, and is a common template for preparing core-shell structure materials.
The adsorption in the step 3) is enhanced adsorption, which is a method for obtaining a precursor of the carbon-coated hollow spheres and/or nanoparticles rich in metal salt ions by putting a composite structure of the carbon-coated hollow spheres and/or nanoparticles and a metal salt solution into a beaker to be adsorbed at a certain water bath temperature, regulating the pH value of the salt solution and a solvent system so as to enhance the adsorption of the carbon layer coated on the hollow spheres and/or nanoparticles on the metal ions at a proper temperature, a proper solvent system and a proper pH value state, and cooling, centrifuging, washing and drying the precursor.
In the roasting in the step 4), the metal salt adsorbed on the carbon surface of the hollow spheres and/or the nano particles is gradually solidified and coated by controlling the heating rate, the heat preservation time and the oxygen concentration in the furnace chamber, and the carbon layer is contracted and oxidized and combusted, so that the metal oxide with the multi-shell structure is formed while the carbon layer template is slowly removed. This method of preparing multi-shell oxides is referred to as the "sequential templating method".
Preferably, the hollow spheres in step 1) include one or a combination of two or more of titanium dioxide, silicon dioxide, germanium dioxide, tin dioxide, lead dioxide, cerium dioxide, vanadium pentoxide, chromium sesquioxide, manganese dioxide, iron sesquioxide, ferroferric oxide, cobaltosic oxide, cobaltous oxide, nickel oxide, copper oxide, cuprous oxide, zinc oxide, niobium pentoxide, tantalum pentoxide, molybdenum trioxide, tungsten trioxide, calcium oxide, calcium carbonate, strontium titanate, barium titanate, gold, and silicon; preferably one or the combination of any two or more of titanium dioxide, silicon dioxide, tin dioxide, cerium dioxide, vanadium pentoxide, niobium pentoxide, tantalum pentoxide, calcium oxide, calcium carbonate, strontium titanate, barium titanate, gold and silicon; further preferably one or a combination of any two or more of titanium dioxide, tin dioxide, cerium dioxide, niobium pentoxide, tantalum pentoxide, gold and silicon;
preferably, the nanoparticles in step 1) include one or a combination of two or more of titanium dioxide, silicon dioxide, germanium dioxide, tin dioxide, lead dioxide, cerium dioxide, vanadium pentoxide, chromium sesquioxide, manganese dioxide, iron sesquioxide, ferroferric oxide, cobaltosic oxide, cobaltous oxide, nickel oxide, copper oxide, cuprous oxide, zinc oxide, niobium pentoxide, tantalum pentoxide, molybdenum trioxide, tungsten trioxide, calcium oxide, calcium carbonate, strontium titanate, barium titanate, gold, and silicon; preferably one or the combination of any two or more of titanium dioxide, silicon dioxide, tin dioxide, cerium dioxide, vanadium pentoxide, niobium pentoxide, tantalum pentoxide, calcium oxide, calcium carbonate, strontium titanate, barium titanate, gold and silicon; further preferably one or a combination of any two or more of titanium dioxide, tin dioxide, cerium dioxide, niobium pentoxide, tantalum pentoxide, gold and silicon;
preferably, the surfactant in step 1) comprises one or more of polyvinylpyrrolidone, octadecyl trimethyl ammonium bromide, polyethylene glycol, sodium dodecyl sulfate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polyoxyethylene polyoxypropylene ether block copolymer; preferably polyvinylpyrrolidone; further preferred is polyvinylpyrrolidone of type K13-K80.
The concentration of the surfactant is 1 to 10-5-1.5*10-4mM, e.g. 1X 10-5mM、2*10-5mM、3*10-5mM、4*10-5mM、5*10-5mM、6*10-5mM、7*10-5mM、8*10-5mM、9*10-5mM、1*10-4mM、1.1*10-4mM、1.2*10-4mM、1.3*10-4mM、1.4*10-4mM or 1.5 x 10-4mM, preferably 3X 10-5mM-1.2*10-4mM, more preferably 6X 10-5mM-1*10-4mM。
The concentration of the hollow spheres and/or nanoparticles is 3 x 10-3-3*10-2mM, e.g. 3X 10- 3mM、6*10-3mM、9*10-3mM、1.2*10-2mM、1.5*10-2mM、1.8*10-2mM、2.1*10-2mM、2.4*10-2mM、2.7*10-2mM or 3 x 10-2mM, preferably 3X 10-3mM-1.8*10-2mM。
Preferably, the step 1) stirring modification, stirring temperature is 15-70 ℃, for example, can be 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, preferably 25-55 ℃, more preferably 25-40 ℃.
The stirring time is 2 to 24 hours, and may be, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, preferably 6 to 20M, and more preferably 12 to 20 hours.
The number of washing is 2 to 5, and for example, 2, 3, 4 or 5, preferably 3 to 4.
Preferably, the carbon source in step 2) comprises one or more of glucose, fructose, sucrose, maltose, starch and citric acid; further preferably glucose.
The concentration of the carbon source in the aqueous carbon source solution is 0.1 to 4M, and may be, for example, 0.1M, 0.5M, 1M, 1.5M, 2M, 2.5M, 3M, 3.5M or 4M, preferably 0.5 to 3M, and more preferably 1 to 2.5M.
The concentration of the hollow spheres and/or the nanoparticles is 2 x 10-3-2*10-2mM, e.g. 2X 10-3mM、4*10-3mM、6*10-3mM、8*10-3mM、1*10-2mM、1.2*10- 2mM、1.4*10-2mM、1.6*10-2mM、1.8*10-2mM or 2 x 10-2mM, preferably 4X 10-3mM-1.6*10-2mM。
Preferably, the heating reaction in step 2) is a hydrothermal reaction, and the temperature of the hydrothermal reaction is 160-220 ℃, for example, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ or 220 ℃, more preferably 165-195 ℃;
the hydrothermal reaction time is 3 to 7 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 or 7 hours, more preferably 3.5 to 6 hours, and still more preferably 3.5 to 5 hours;
the drying temperature is 60-100 deg.C, such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C, more preferably 70-90 deg.C, and still more preferably 70-85 deg.C;
the drying time is 6-24h, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, more preferably 10-22h, and still more preferably 10-16 h;
washing with one or more of deionized water, methanol, ethanol or isopropanol; for example, deionized water, methanol, ethanol, isopropanol, a combination of deionized water and methanol, a combination of deionized water and ethanol, a combination of deionized water and isopropanol, or a combination of methanol and ethanol.
The number of washing is 2 to 5, and for example, 2, 3, 4 or 5, preferably 3 to 4.
Preferably, the metal salt in step 3) includes one or more of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt sulfate, manganese acetate, manganese nitrate, manganese chloride, manganese sulfate, nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxalate, iron chloride, iron nitrate, ferric sulfate, titanium tetrachloride, tetrabutyl titanate, methyl orthosilicate, ethyl orthosilicate, ammonium metavanadate, stannic chloride, stannous sulfate, stannic oxalate, stannous acetate, cerium chloride, cerium nitrate, cerium sulfate, cerium acetate, calcium chloride, calcium nitrate and calcium sulfate; further preferably one or more of cobalt chloride, cobalt acetate, manganese chloride, nickel acetate, zinc nitrate, zinc acetate, ferric chloride, ferric nitrate, titanium tetrachloride, cerium chloride and cerium nitrate; a metal salt, more preferably one or a combination of two or more of cobalt acetate, manganese acetate, nickel acetate, zinc acetate and ferric chloride;
the concentration of the metal salt solution is 0.01 to 5M, and may be, for example, 0.01M, 0.1M, 0.2M, 0.5M, 1M, 2M, 3M, 4M or 5M, more preferably 0.05 to 3M, and still more preferably 0.1 to 2M;
wherein, the solvent of the metal salt solution comprises one or more than two of water, acetone and ethanol. Further preferably water and/or ethanol.
Preferably, the adsorption in the step 2) is heat-preservation stirring adsorption;
the adsorption temperature is 20-70 deg.C, such as 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C or 70 deg.C, preferably 25-60 deg.C, more preferably 25-40 deg.C;
the adsorption time is 0.5 to 36 hours, more preferably 0.5 to 28 hours, and still more preferably 0.5 to 24 hours;
after adsorption, carrying out suction filtration and cleaning on the mixed solution obtained by adsorption; washing with one or the combination of more than two of deionized water, methanol, ethanol and isopropanol; for example, deionized water, methanol, ethanol, isopropanol, a combination of deionized water and methanol, a combination of deionized water and ethanol, a combination of deionized water and isopropanol, or a combination of methanol and ethanol; the number of washing is 2 to 5, for example, 2, 3, 4 or 5, and more preferably 3 to 4; the washing time is 0.5 to 24 hours, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 11 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, more preferably 5 to 20 hours, and still more preferably 10 to 15 hours;
the drying temperature is 60-100 deg.C, such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C, more preferably 70-90 deg.C, and still more preferably 70-85 deg.C;
the drying time is 6-24h, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, more preferably 10-22h, and still more preferably 10-16 h;
preferably, the roasting in step 4) is performed in a muffle furnace, a tube furnace or a kiln furnace;
the baking temperature is 180-
The calcination time is 0.5 to 10 hours, and for example, it may be 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours or 10 hours, more preferably 1 to 6 hours, still more preferably 2 to 4 hours;
the heating rate of the calcination is 0.1 to 20 ℃/min, and for example, it may be 0.5 ℃/min, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min or 10 ℃/min, more preferably 0.5 to 10 ℃/min, still more preferably 1 to 10 ℃/min;
the roasting atmosphere is air, oxygen or a mixed gas of nitrogen and oxygen, and the proportion of oxygen in the mixed gas of nitrogen and oxygen is 5% -40%, for example, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%. More preferably, the volume ratio of oxygen in the mixed gas of nitrogen and oxygen is 10% to 30%, and still more preferably 15% to 25%.
According to the invention, by regulating and controlling conditions such as modification concentration, modification temperature and modification time of the surfactant, regulating and controlling material proportion, hydrothermal temperature and hydrothermal time in a hydrothermal carbonization process, and carrying out ion collocation on the carbon-coated hollow spheres and/or nanoparticles, a hollow composite structure with a plurality of hollow spheres and/or nanoparticles coated by a plurality of shells can be obtained, the hollow spheres and/or nanoparticles in the hollow composite structure can be randomly collocated, and the metal oxide shell layer outside the hollow composite structure can also be randomly regulated and controlled. The internally loaded hollow spheres and/or nanoparticles can have the energy density of a composite structure, and the multi-shell structure can relieve the volume expansion of the hollow spheres and/or nanoparticles in the lithiation/delithiation process, so that the energy density is improved, and the stable circulation of the material can be realized; the thin shell layer can shorten the transmission path of ions and electrons, and greatly improves the rate capability of the material.
The invention provides a composite hollow structure material with a plurality of hollow spheres and/or nano particles coated by a plurality of shells, which is obtained by the preparation method.
The multi-shell material comprises at least one cavity and at least one shell wall, and the number of the hollow spheres and/or the nanoparticles can be at least two hollow spheres, at least two nanoparticles, or a combination of at least one hollow sphere and at least one nanoparticle;
wherein, the shell layer is preferably but not limited to one or more than two of metal oxide, metal sulfide and metal phosphide. The inner core is preferably, but not limited to, including one or a combination of any two or more of silicon, titanium dioxide, tin dioxide, cerium dioxide, niobium pentoxide, and tantalum pentoxide;
the shell wall is 2-4 layers, for example, 2 layers, 3 layers or 4 layers;
the invention provides an application of a composite hollow structure material with a plurality of hollow spheres and/or nanoparticles coated by a plurality of shells in energy storage, and provides a composite structure material for a lithium ion battery cathode, wherein the composite structure material for the lithium ion battery cathode comprises a material which encapsulates the hollow spheres and/or nanoparticles in the hollow structure, namely the composite hollow structure material with the hollow spheres and/or nanoparticles coated by the shells;
the composite structure material for the lithium ion battery cathode can stably circulate for more than 700 circles in a voltage range of 0-3V at a current density of 2A/g and still can maintain the specific capacity of 1200 mAh/g.
Compared with the prior art, the invention has the following beneficial effects:
1) when the multi-shell coated hollow sphere and/or nano particle hollow material prepared by the invention is applied to the negative electrode of a lithium ion battery, the material shows better cycle stability in the high-rate charge and discharge process. The hollow sphere and/or the nano-particles of the inner core can improve the energy density per unit volume of the multi-shell layer, and the existence of the multi-shell metal oxide layer can effectively buffer the volume expansion in the charging and discharging processes, thereby ensuring the cycling stability of the material; but also shorten the transmission path of lithium ions and electrons. The material can still maintain 1200mAh/g specific capacity after being stably circulated for more than 700 circles in a voltage range of 0-3V by a current density of 2A/g, the performance of the material is far superior to that of a hollow structure with the same structure, and the stability of the material is far superior to that of a material directly mixed with the same components.
2) The hollow sphere and/or the nano particle are distributed in the multi-shell due to the unique hierarchical structure of the multi-shell coated hollow sphere and/or nano particle hollow material, compared with the multi-layer hollow sphere, the volume capacity density of the material is greatly increased, the prepared electrode material has higher energy density, and the light-weight requirement of an energy storage device is met.
Drawings
FIG. 1 is a transmission electron micrograph of a material prepared in example 1 of the present invention;
FIG. 2 is an EDX mapping element distribution picture of a transmission electron microscope of the material prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscopy brightfield photograph of the material prepared in example 2 of the present invention;
FIG. 4 is a graph of the battery cycle performance of the material prepared in example 2 of the present invention;
FIG. 5 is a TEM image of the material prepared in example 3 of the present invention;
FIG. 6 is a TEM image of a material prepared in example 4 of the present invention;
FIG. 7 is a TEM image of the material prepared in example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The invention provides a preparation method of a composite hollow structure material with a plurality of hollow spheres and/or nanoparticles coated by a plurality of shells, which comprises the following steps:
(a) the concentration is 3 x 10-3-3*10-2Adding mM hollow spheres and/or nanoparticles to a concentration of 1 × 10-5-1.5*10- 4In the mM surfactant, the hollow sphere and/or the nanoparticle is one or the combination of more than two of titanium dioxide, tin dioxide, cerium dioxide, niobium pentoxide, tantalum pentoxide, gold and silicon, the stirring temperature is 15-70 ℃, the stirring time is 2-24h, and after 2-5 times of centrifugal washing, the hollow sphere and/or the nanoparticle modified by the surfactant is obtained;
(b) preparing the surfactant-modified hollow spheres and/or nanoparticles obtained in the step (a) into the surfactant-modified hollow spheres and/or nanoparticles with the concentration of 2 x 10-3-2*10-2Adding the mM carbon source into 0.1-4M carbon source aqueous solution, then putting the mixture into a hydrothermal reaction kettle for hydrothermal reaction for 3-7h at the temperature of 160-220 ℃, naturally cooling, performing suction filtration, washing for 2-5 times, and drying the product for 6-24h at the temperature of 60-100 ℃ to obtain the composite material of the carbon-coated hollow spheres and/or nanoparticles;
(c) dispersing the composite material of the carbon-coated hollow spheres and/or nanoparticles obtained in the step (b) in a metal salt solution with the concentration of 0.01-5M to obtain a suspension. Wherein the metal salt solution is one or a combination of more than two of cobalt acetate, manganese acetate, nickel acetate, zinc acetate and ferric chloride, is adsorbed for 0.5h-36h at the temperature of 20-70 ℃, the adsorbed mixed solution is filtered, washed for 2-5 times by deionized water, methanol or ethanol, and dried for 6-24h at the temperature of 60-100 ℃ to obtain a solid precursor;
(d) and (c) placing the solid precursor obtained in the step (c) in a muffle furnace or a kiln, roasting for 0.5-10h in air, oxygen or an atmosphere with the oxygen proportion of 5-40% in a mixed gas of oxygen and nitrogen, wherein the roasting temperature is 200-600 ℃, the heating rate is 0.1-20 ℃/min, and cooling to obtain the multi-shell coated multi-hollow sphere and/or nano particle composite material.
Example 1
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 3 x 10-3Adding the mM titanium dioxide and niobium pentoxide hollow spheres to the concentration of 1 x 10-5Stirring at 25 ℃ for 12h in mM polyvinylpyrrolidone (type K29), and centrifuging and washing for 3 times to obtain surfactant-modified titanium dioxide and niobium pentoxide hollow spheres;
(2) preparing the titanium dioxide and niobium pentoxide hollow spheres modified by the surfactant obtained in the step (1) into hollow spheres with the concentration of 2 x 10-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of carbon-coated titanium dioxide and niobium pentoxide hollow spheres with the diameter of 1 micron;
(3) and (3) dispersing the material of the carbon-coated titanium dioxide and niobium pentoxide hollow spheres obtained in the step (2) into a cobalt acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 30 ℃ for adsorption for 12h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated titanium dioxide and niobium pentoxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated multiple titanium dioxide and niobium pentoxide hollow sphere solid precursor obtained in the step (3) into a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min, calcining for 2h at constant temperature in the atmosphere of air, and naturally cooling to obtain the double-shell cobalt manganese oxide-coated multiple titanium dioxide and niobium pentoxide hollow sphere composite material.
The transmission electron micrograph and TEM-EDX mapping of the product are shown in figures 1 and 2, and the product is a composite material of a plurality of titanium dioxide and niobium pentoxide hollow spheres coated by double-shell cobalt manganese oxide. As can be seen from the figure, a plurality of hollow spheres are distributed inside the double-shell layer; the EM-EDX mapping element analysis shows that the cobalt and manganese elements are uniformly distributed on the outer shell layer, and the niobium element and the titanium element are distributed inside.
Example 2
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 1 x 10-2mM silicon nanoparticles were added to a concentration of 3 x 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 30 deg.C for 24 hr, and centrifuging for 3 times to obtain surfactant-modified silicon nanoparticles;
(2) preparing the surfactant modified silicon nanoparticles obtained in the step (1) into silicon nanoparticles with the concentration of 2 x 10-3Adding mM into 1.8M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 180 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain a material with the diameter of 0.9 micron and coated with a plurality of silicon nano-particles by carbon;
(3) and (3) dispersing the carbon-coated silicon nanoparticles obtained in the step (2) in a ferric chloride solution with the concentration of 1M and a cobalt acetate solution with the concentration of 0.3M to obtain a suspension. Keeping the temperature at 30 ℃ for adsorption for 24h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a carbon-coated silicon nanoparticle solid precursor;
(4) and (4) placing the carbon-coated multi-silicon-nanoparticle solid precursor obtained in the step (3) in a muffle furnace, heating to 450 ℃ at a speed of 4 ℃/min, calcining for 2 hours at a constant temperature in the presence of air, and naturally cooling to obtain the double-shell cobalt-iron oxide-coated multi-silicon-nanoparticle composite material.
FIG. 3 is a transmission electron microscopy brightfield photograph of the material prepared in example 2 of the present invention; FIG. 4 shows the cycle performance of the charge and discharge test performed in the voltage range of 0-3V when the above material is used for the negative electrode of a lithium ion battery. Thanks to the superiority of the material structure, the assembled battery can be cycled for 700 cycles at a current density of 2A/g and can maintain 1200mAh/g, and the huge potential of the material for high-capacity long-cycle lithium ion batteries is shown.
Example 3
A method of preparing a composite hollow structure hollow material having a plurality of hollow spheres and/or nanoparticles coated with a multi-shell, the method comprising:
(1) the concentration is 5 x 10-3Adding mM niobium pentoxide hollow ball with concentration of 2 x 10-5Stirring at 30 ℃ for 24 hours in mM polyvinylpyrrolidone (type K29), and centrifuging and washing for 3 times to obtain surfactant-modified niobium pentoxide hollow spheres;
(2) preparing the surfactant modified niobium pentoxide hollow spheres obtained in the step (1) into 2 x 10-concentration hollow spheres-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of the carbon-coated niobium pentoxide hollow spheres with the diameter of 0.95 microns;
(3) and (3) dispersing the carbon-coated niobium pentoxide hollow ball materials obtained in the step (2) in 0.3M cobalt acetate and 0.15M nickel acetate solution to obtain a suspension. Keeping the temperature at 30 ℃ for adsorption for 12h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated niobium pentoxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated multiple niobium pentoxide hollow sphere solid precursor obtained in the step (3) into a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min, calcining for 2 hours at a constant temperature in the atmosphere of air, and naturally cooling to obtain the composite material of the three-shell nickel-cobalt oxide-coated multiple niobium pentoxide hollow spheres.
FIG. 5 is a TEM image of the material prepared in example 3 of the present invention; as can be seen from the figure, the outer layer is three-shell nickel-cobalt oxide, and the innermost layer is distributed with a plurality of niobium pentoxide hollow spheres.
Example 4
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 5 x 10-3Adding the mM titanium dioxide hollow sphere to the concentration of 2 x 10-5In mM ofStirring polyvinylpyrrolidone (type K29) at 25 deg.C for 12h, and centrifuging for 3 times to obtain surfactant-modified hollow titanium dioxide spheres;
(2) preparing the titanium dioxide hollow spheres modified by the surfactant obtained in the step (1) into titanium dioxide hollow spheres with the concentration of 2 x 10-3Adding mM into 1.5M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4.5h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product for 20h at 70 ℃ to obtain the material with the diameter of 0.85 micron and coating a plurality of titanium dioxide hollow spheres with carbon;
(3) and (3) dispersing the carbon-coated titanium dioxide hollow spheres obtained in the step (2) in a cobalt acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 30 ℃ for 12h for adsorption, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated titanium dioxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated multiple titanium dioxide hollow sphere solid precursor obtained in the step (3) in a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, calcining for 2 hours at a constant temperature in the presence of air, and naturally cooling to obtain the composite material with multiple titanium dioxide hollow spheres coated with the three-shell cobalt-manganese oxide.
FIG. 6 is a TEM image of a material prepared in example 4 of the present invention; as can be seen from the figure, the outer layer is three-shell manganese cobalt oxide, and a plurality of titanium dioxide hollow spheres are distributed on the innermost layer.
Example 5
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 5 x 10-3Adding the mM titanium dioxide hollow sphere to the concentration of 2 x 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 30 deg.C for 12 hr, and centrifuging for 3 times to obtain surfactant-modified hollow titanium dioxide spheres;
(2) preparing the titanium dioxide hollow spheres modified by the surfactant obtained in the step (1) into titanium dioxide hollow spheres with the concentration of 5 x 10-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of a plurality of carbon-coated titanium dioxide hollow spheres with the diameter of 1 micron;
(3) and (3) dispersing the carbon-coated titanium dioxide hollow spheres obtained in the step (2) in a cobalt acetate solution with the concentration of 0.3M and a nickel acetate solution with the concentration of 0.15M to obtain a suspension. Keeping the temperature at 30 ℃ for 12h for adsorption, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated titanium dioxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated multiple titanium dioxide hollow sphere solid precursor obtained in the step (3) in a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, calcining for 2 hours at a constant temperature in the presence of air, and naturally cooling to obtain the double-shell nickel-cobalt oxide-coated multiple titanium dioxide hollow sphere composite material.
FIG. 7 is a TEM image of a material prepared in example 5 of the present invention; as can be seen from the figure, the outer layer is double-shell nickel-cobalt oxide, and a plurality of titanium dioxide hollow spheres are distributed on the innermost layer.
Example 6
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 1 x 10-2mM silicon nanoparticles were added to a concentration of 3 x 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 30 deg.C for 24 hr, and centrifuging for 3 times to obtain surfactant-modified silicon nanoparticles;
(2) preparing the surfactant modified silicon nano-particles obtained in the step (1) into silicon nano-particles with the concentration of 1 x 10-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain a material with the diameter of 1 micron and coated with a plurality of silicon nanoparticles;
(3) and (3) dispersing the carbon-coated silicon nanoparticles obtained in the step (2) in a cobalt acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 30 ℃ for adsorption for 24h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a carbon-coated silicon nanoparticle solid precursor;
(4) and (4) placing the carbon-coated multiple silicon nanoparticle solid precursor obtained in the step (3) in a muffle furnace, heating to 400 ℃ at the speed of 1 ℃/min, calcining for 2 hours at constant temperature in the atmosphere of air, and naturally cooling to obtain the three-shell cobalt-manganese oxide-coated multiple silicon nanoparticle composite material.
Example 7
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 5 x 10-3The mM titanium dioxide nanoparticles were added at a concentration of 2X 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 30 deg.C for 12 hr, and centrifuging for 3 times to obtain surfactant-modified titanium dioxide nanoparticles;
(2) preparing the titanium dioxide nano particles modified by the surfactant obtained in the step (1) into nano particles with the concentration of 5 x 10-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain a material with a plurality of carbon-coated titanium dioxide nanoparticles with the diameter of 1 micron;
(3) dispersing the carbon-coated titanium dioxide nanoparticles obtained in the step (2) in a zinc acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 30 ℃ for 12h for adsorption, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated titanium dioxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated titanium dioxide hollow sphere nanoparticle solid precursor obtained in the step (3) in a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, calcining for 2 hours at constant temperature in the atmosphere of air, and naturally cooling to obtain the double-shell zinc-manganese oxide-coated titanium dioxide nanoparticle composite material.
Example 8
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 5 x 10-3Adding mM stannic oxide hollow sphere to the concentration of 2 x 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 35 deg.C for 10 hr, and centrifuging for 3 times to obtain surfactant-modified hollow tin dioxide spheres;
(2) preparing the surfactant modified stannic oxide hollow sphere obtained in the step (1) into a stannic oxide hollow sphere with the concentration of 5 x 10-3Adding mM into 1M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of a plurality of carbon-coated tin dioxide hollow spheres with the diameter of 1 micron;
(3) and (3) dispersing the plurality of carbon-coated tin dioxide hollow spheres obtained in the step (2) in a ferric chloride solution with the concentration of 1M and a cobalt acetate solution with the concentration of 0.3M to obtain a suspension. Keeping the temperature at 30 ℃ for 12h for adsorption, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a plurality of carbon-coated tin dioxide hollow sphere solid precursors;
(4) and (4) placing the carbon-coated tin dioxide hollow sphere solid precursor obtained in the step (3) in a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, calcining for 2 hours at constant temperature in the atmosphere of air, and naturally cooling to obtain the double-shell cobalt-iron oxide-coated tin dioxide hollow sphere composite material.
Example 9
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 4 x 10-3Adding hollow balls of mM titanium dioxide, tantalum pentoxide and niobium pentoxide to the concentration of 1 × 10-5Stirring in mM polyvinylpyrrolidone (type K29) at 25 deg.C for 12 hr,and after 3 times of centrifugal washing, the titanium dioxide, tantalum pentoxide and niobium pentoxide hollow spheres modified by the surfactant are obtained;
(2) preparing the titanium dioxide, tantalum pentoxide and niobium pentoxide hollow spheres modified by the surfactant obtained in the step (1) into hollow spheres with the concentration of 2 x 10-3Adding mM into 1.8M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of carbon-coated titanium dioxide, tantalum pentoxide and niobium pentoxide hollow spheres with the diameter of 0.8 micron;
(3) and (3) dispersing the material of the carbon-coated titanium dioxide, tantalum pentoxide and niobium pentoxide hollow spheres obtained in the step (2) into a cobalt acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 35 ℃ for adsorption for 24h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ oven for drying for 20h to obtain a carbon-coated solid precursor of a plurality of titanium dioxide, tantalum pentoxide and niobium pentoxide hollow spheres;
(4) and (4) placing the carbon-coated multiple titanium dioxide, tantalum pentoxide and niobium pentoxide hollow sphere solid precursor obtained in the step (3) into a muffle furnace, heating to 400 ℃ at the speed of 2 ℃/min, calcining for 2h at constant temperature in the atmosphere of air, and naturally cooling to obtain the double-shell cobalt manganese oxide-coated multiple titanium dioxide, tantalum pentoxide and niobium pentoxide hollow sphere composite material.
Example 10
A method of making a composite hollow structure having a plurality of hollow spheres and/or nanoparticles coated with a multishell, the method comprising:
(1) the concentration is 4 x 10-3Adding mM silicon nano-particles and cerium dioxide hollow spheres to the concentration of 1 × 10-5Stirring at 25 ℃ for 12h in mM polyvinylpyrrolidone (type K29), and centrifuging and washing for 3 times to obtain surfactant-modified silicon nanoparticles and cerium dioxide hollow spheres;
(2) preparing the silicon nano particles modified by the surfactant obtained in the step (1) and cerium dioxide hollow spheres into a concentrated solutionDegree 4 x 10-3Adding mM into 2M glucose aqueous solution, then putting into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4h at 170 ℃, naturally cooling, carrying out suction filtration, washing for 3 times, and drying the product at 70 ℃ for 20h to obtain the material of carbon-coated silicon nanoparticles and cerium dioxide hollow spheres with the diameter of 0.85 micron;
(3) and (3) dispersing the material of the carbon-coated silicon nano particles and the cerium dioxide hollow spheres obtained in the step (2) in a zinc acetate and manganese acetate solution with the concentration of 0.8M to obtain a suspension. Keeping the temperature at 35 ℃ for adsorption for 24h, carrying out suction filtration after adsorption, washing with deionized water for 3 times, and then putting into a 70 ℃ drying oven for drying for 20h to obtain a plurality of carbon-coated silicon nanoparticles and a ceria hollow sphere solid precursor;
(4) and (4) placing the carbon-coated silicon nanoparticles and the cerium dioxide hollow sphere solid precursor obtained in the step (3) in a muffle furnace, heating to 400 ℃ at the speed of 2 ℃/min, calcining for 2h at constant temperature in the atmosphere of air, and naturally cooling to obtain the double-shell zinc-manganese oxide-coated silicon nanoparticle and cerium dioxide hollow sphere composite material.
The invention takes a plurality of materials with different hollow sphere structures or nano particle structures as cores, and the outside is a hierarchical structure with a multi-shell layer hollow structure. The preparation method comprises the steps of modifying a material with a hollow structure or a nano-particle structure by a surfactant, embedding a plurality of hollow spheres and/or nano-particles inside by utilizing a carbon source in a hydrothermal process, roasting after a surface carbon layer adsorbs metal ions, forming external multi-shell layers by the metal ions of the carbon layer in a sequential template method in the roasting process, keeping an internal core inside, and finally preparing the hollow composite structure with the plurality of hollow spheres and/or nano-particles coated by the multi-shell.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
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| CN108085241A (en) * | 2018-01-25 | 2018-05-29 | 吉林冠界生物技术有限公司 | Powder material throwing device and the tank body containing described device |
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| CN115377377A (en) * | 2022-08-05 | 2022-11-22 | 湖州永兴新能源有限公司 | Lithium-niobium-titanium cathode-lithium manganese iron phosphate anode lithium ion battery |
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| CN115925001A (en) * | 2022-12-22 | 2023-04-07 | 浙江大学山东工业技术研究院 | Ta 2 O 5 /NiO composite hollow nanosphere material and preparation method and application thereof |
| CN115925001B (en) * | 2022-12-22 | 2024-06-04 | 浙江大学山东工业技术研究院 | Ta2O5/NiO composite hollow nanosphere material and its preparation method and application |
| CN116372096A (en) * | 2023-05-26 | 2023-07-04 | 山东昊普机械制造有限公司 | Coating for lost foam casting and preparation process thereof |
| CN116372096B (en) * | 2023-05-26 | 2023-08-08 | 山东昊普机械制造有限公司 | Coating for lost foam casting and preparation process thereof |
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