CN112768656A - Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof - Google Patents
Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof Download PDFInfo
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- CN112768656A CN112768656A CN202110033317.5A CN202110033317A CN112768656A CN 112768656 A CN112768656 A CN 112768656A CN 202110033317 A CN202110033317 A CN 202110033317A CN 112768656 A CN112768656 A CN 112768656A
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- Prior art keywords
- transition metal
- metal sulfide
- carbon
- coated
- salt
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 127
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 48
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000571 coke Substances 0.000 claims abstract description 14
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000005720 sucrose Substances 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002751 molybdenum Chemical class 0.000 claims description 3
- 150000003681 vanadium Chemical class 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
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001462 antimony Chemical class 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
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000003657 tungsten Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 4
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 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 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a carbon-coated mesoporous transition metal sulfide negative electrode material and a preparation method and application thereof. The preparation method comprises the steps of mixing polyvinylpyrrolidone, a transition metal salt solution and a sulfur source, and heating until the reaction is finished to obtain a transition metal-containing sulfide solution; uniformly mixing a transition metal sulfide-containing solution with a carbon source and then reacting to obtain a transition metal sulfide coated by coke; centrifuging, cleaning and drying the transition metal sulfide coated by the coke to obtain solid transition metal sulfide powder; and calcining the solid transition metal sulfide powder in an inert atmosphere to obtain the carbon-coated mesoporous transition metal sulfide negative electrode material. The cathode material is formed by stacking a plurality of nanoscale primary particles, the primary particles are composed of transition metal sulfides in the inner layer and amorphous carbon coating layers coated on the surfaces of the transition metal sulfides, and a mesoporous structure is formed among the plurality of primary particles. The material of the invention has high structural stability and simple preparation method.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a carbon-coated mesoporous transition metal sulfide negative electrode material and a preparation method and application thereof.
Background
Energy storage devices such as lithium ion batteries and sodium ion batteries have the excellent characteristics of no pollution, high specific energy, high working voltage, long cycle life, no memory effect and the like, and are widely applied to various energy fields such as portable equipment and mobile power supplies. At present, negative electrode materials of lithium ion and sodium ion batteries widely used in commercialization mainly comprise graphite, lithium titanate and the like, but the traditional negative electrode materials are low in theoretical specific capacity and cannot meet the development requirements of secondary batteries with high capacity, high power and long service life.
Based on the defects of the existing battery cathode materials, research and development personnel try to develop a new cathode material. The transition metal sulfide is beneficial to the deintercalation of lithium ions and sodium ions, and the sulfide-based negative electrode material has the advantage of higher specific capacity, so that the transition metal sulfide is widely concerned by research personnel. For example, patent document CN108075128A discloses a nitrogen-doped carbon-coated cobalt-nickel sulfide/graphene composite electrode material, in which an organic ligand is carbonized to form carbon through a one-step carbonization and sulfurization process, and nitrogen is doped into the carbon formed by the organic ligand in sulfurization, so as to improve the conductivity and defects of the electrode material, thereby improving the electrochemical performance. However, since cobalt-nickel sulfide particles are loaded on the graphene substrate, and the relative positions of the particles are fixed, the cobalt-nickel sulfide particles as an electrode material cannot effectively relieve the volume expansion of transition metal sulfides in the use process, so that the discharge specific capacity and the rate capability of the battery are obviously deteriorated in the later use period. For another example, patent document CN112018344A discloses a carbon-coated nickel sulfide electrode material, which is capable of buffering the volume change of the material caused by the sodium ion deintercalation process by forming an amorphous carbon coating layer on the surface of nickel disulfide, but the volume change of the carbon coating layer coated on the surface of nickel disulfide can be buffered only to a certain extent due to its thickness and stretchability of the carbon coating layer, and the structure and electrochemical stability of the material during use cannot be completely ensured.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, an object of the present invention is to solve the technical problem of the deterioration of specific discharge capacity and rate capability due to the volume expansion of transition metal sulfide, and to provide a carbon-coated mesoporous transition metal sulfide negative electrode material having a mesoporous structure and an amorphous carbon coating layer cooperating with each other to ensure high structural and electrochemical stability.
One aspect of the invention provides a preparation method of a carbon-coated mesoporous transition metal sulfide negative electrode material, which comprises the following steps: mixing polyvinylpyrrolidone, a transition metal salt solution and a sulfur source, and heating until the reaction is finished to obtain a transition metal sulfide-containing solution; uniformly mixing a transition metal sulfide-containing solution with a carbon source, and heating until the reaction is finished to obtain a transition metal sulfide coated by coke; centrifuging, cleaning and drying the transition metal sulfide coated by the coke to obtain solid transition metal sulfide powder; and calcining the solid transition metal sulfide powder in an inert atmosphere to obtain the carbon-coated mesoporous transition metal sulfide negative electrode material.
Another aspect of the present invention provides a carbon-coated mesoporous transition metal sulfide anode material prepared by the above method, which may be formed by stacking a plurality of nanoscale primary particles, wherein the primary particles are composed of an inner layer of transition metal sulfide and an amorphous carbon coating layer coated on the surface of the transition metal sulfide, and a mesoporous structure is formed between the plurality of primary particles.
The invention further provides application of the carbon-coated mesoporous transition metal sulfide negative electrode material in lithium ion batteries, sodium ion batteries and lithium sulfur batteries.
The principle of the carbon-coated mesoporous transition metal sulfide negative electrode material comprises the following steps: in one aspect, polyvinylpyrrolidone has a hydrophobic vinyl group and a hydrophilic carboxyl group that can lead to the formation of polarized nuclei. The crystal nuclei formed in the early stage of the transition metal sulfide are adsorbed on the carboxyl group of polyvinylpyrrolidone and then gradually and closely packed together. With further reaction, these nanocrystallites are stacked into monodisperse transition metal sulfide nanospheres by the LaMer mechanism. In the reaction process, the polyvinylpyrrolidone plays an important role in adjusting the morphology and preventing the particles from agglomerating, which is mainly due to the steric hindrance effect generated by the hydrophobic carbon chains of the polyvinylpyrrolidone, and the effect effectively hinders the agglomeration of the particles so that a mesoporous mechanism is formed between the particles; on the other hand, the carbon source can be uniformly attached to the surface of the transition metal sulfide, and a uniform amorphous carbon coating layer can be formed on the surface of the transition metal sulfide after the calcination treatment. The formed mesopores can provide enough space to relieve the abrupt change of the material volume caused by lithium ions or sodium ions and the like in the de-intercalation process, and can further increase active sites so as to store lithium or sodium; the formed amorphous carbon coating is coated on the surface of the transition metal sulfide particles, and is matched with the formed mesopores, so that the volume effect of the transition metal sulfide can be completely avoided under the synergistic effect, and the structure and the electrochemical stability of the transition metal sulfide can be kept in the using process.
Due to the adoption of the technical scheme, the invention has at least one of the following advantages:
(1) the carbon-coated mesoporous sulfide electrode material has a mesoporous structure capable of buffering the abrupt change of the volume of the material in the lithium or sodium ion extraction process, can ensure the structural and electrochemical stability of the electrode material in the use process, and can ensure that the excellent specific capacity and high rate performance are continuously maintained in the use process.
(2) The amorphous carbon coating layer formed on the surface of the carbon-coated mesoporous sulfide electrode material can relieve the volume effect of transition metal sulfide and improve the conductivity of the electrode material.
(3) The mesoporous structure of the carbon-coated mesoporous sulfide electrode material has the synergistic effect with the surface-coated amorphous carbon, so that the influence on the structure and chemical stability of the material due to the volume change of the material can be almost completely avoided.
(4) The carbon-coated mesoporous transition metal sulfide negative electrode material is prepared by a hydrothermal method and a high-temperature heat treatment method, the operation is simple, and the size of the prepared negative electrode material reaches dozens of to hundreds of nanometers, the purity is high, the crystallinity is strong, and the shape is uniform; the preparation repeatability is high, the yield is high, the product structure is easy to control, and the method is suitable for industrial popularization.
(5) The carbon-coated mesoporous transition metal sulfide negative electrode material has long cycle life, high charge-discharge capacity and rate capability, can meet the actual application requirements of high-performance battery preparation, and has very wide application prospects in the battery field.
Drawings
FIG. 1 is a morphology of an exemplary carbon-coated metal sulfide anode material of the present invention 1;
FIG. 2 is a charge-discharge curve diagram of a lithium ion battery assembled by the carbon-coated metal sulfide negative electrode material prepared in example 1 of the present invention at a magnification of 0.1A/g;
fig. 3 is a cycle performance diagram of a lithium ion battery assembled by the carbon-coated metal sulfide negative electrode material prepared in example 1 of the present invention at a rate of 0.1A/g.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
An aspect of the present invention provides a method for preparing a carbon-coated mesoporous transition metal sulfide anode material, which, in an exemplary embodiment of the method for preparing a carbon-coated mesoporous transition metal sulfide anode material, may include:
and S01, mixing the polyvinylpyrrolidone, the transition metal salt solution and the sulfur source, and heating until the reaction is finished to obtain the transition metal-containing sulfide solution.
And S02, uniformly mixing the transition metal sulfide solution with a carbon source, and reacting to obtain the transition metal sulfide coated by the coke.
And S03, centrifuging the transition metal sulfide coated by the coke, cleaning and drying to obtain solid transition metal sulfide powder.
And S04, calcining the solid transition metal sulfide powder in an inert atmosphere to obtain the carbon-coated mesoporous transition metal sulfide negative electrode material.
Further, the transition metal salt is at least one of a nickel salt, a cobalt salt, a manganese salt, a vanadium salt, a molybdenum salt, a tungsten salt, a tin salt, an iron salt, a zinc salt, a copper salt and an antimony salt. During the preparation process, a single salt can be added, and a mixture of multiple salts can also be added. For example, the transition metal salts used are nickel salts and cobalt salts, and the resulting transition metal sulfide is a mixture of nickel sulfide and cobalt sulfide. For another example, the transition metal salt used is a nickel salt, a cobalt salt, a vanadium salt, a molybdenum salt, and a manganese salt, and the obtained transition metal sulfide is a mixture of nickel sulfide, cobalt sulfide, vanadium sulfide, molybdenum sulfide, and manganese sulfide.
In the above, the transition metal salt may be at least one of a sulfate, an acetate, a nitrate and a chloride. For example, for the nickel salt, nickel acetate tetrahydrate, nickel acetate, nickel nitrate, nickel sulfate, or nickel chloride may be mentioned. For example, the cobalt salt may be cobalt chloride, cobalt acetate, cobalt sulfate, or cobalt nitrate.
Further, the sulfur source may be at least one of thiosulfate and thiourea. The thiosulfate can be sodium thiosulfate, potassium thiosulfate and the like.
Furthermore, in the solution obtained by mixing the polyvinylpyrrolidone, the transition metal salt solution and the sulfur source, the concentration of the polyvinylpyrrolidone can be 0.4-0.8 g of polyvinylpyrrolidone in each 100ml of solution. For example, 100ml of the mixed solution contains 0.6g or 0.64g of polyvinylpyrrolidone.
Further, the addition amount of the transition metal salt and the sulfur source can be determined according to the transition metal sulfide to be generated as required. For example, if the transition metal sulfide to be actually generated is nickel sulfide (NiS), the ratio of the amount of the transition metal element contained in the transition metal salt to the amount of the sulfur element in the sulfur source is 1: 1. In the actual preparation process, the thoroughness of the reaction process needs to be considered, so that the amount of the transition metal salt or the sulfur source added may be much larger than appropriate.
Further, the obtaining of the transition metal-containing sulfide solution may further include mixing a transition metal salt solution with a sulfur source and then performing a hydrothermal reaction to obtain the transition metal-containing sulfide solution, wherein the temperature of the hydrothermal reaction may be 160 ℃ to 240 ℃, and the time of the hydrothermal reaction may be 6 hours to 24 hours. For example, the hydrothermal reaction may be carried out at 180 ℃ for 10 hours. For the above-mentioned set reaction temperature is too low, the reaction time is too short, which may result in incomplete reaction, for example, the temperature cannot reach 160 ℃, which may result in the transition metal and the sulfur source not being able to react; the reaction temperature is set to be too high, and the reaction time is too long, so that side reactions can occur.
Further, obtaining the transition metal sulfide-containing solution may further include:
preparing an ethylene glycol aqueous solution;
uniformly mixing polyvinylpyrrolidone with an ethylene glycol aqueous solution, adding a transition metal salt solution and a sulfur source, completely dissolving, and carrying out hydrothermal reaction to obtain a transition metal-containing sulfide solution.
In the above, ethylene glycol is decomposed into acetaldehyde by heating in the hydrothermal reaction process, acetaldehyde can be used as an oxidizing agent for further reaction, and acetaldehyde can be oxidized when a transition metal element with a lower valence state is used as a raw material. For example, with a nickel source of Ni2+Salt as a raw material, Ni2+Oxidation-reduction reaction with oxidant acetaldehyde to produce Ni4+. Further reaction in Ni4+And a sulfur source S2O3 2-The two react to form Ni (S)2O3)2,Ni(S2O3)2Further hydrolyzing to generate NiS final product2。
The polyvinylpyrrolidone can be mixed with the transition metal salt solution and the sulfur source in a dropwise manner. For example, the polyvinyl pyrrolidone may be added dropwise to the ethylene glycol aqueous solution and mixed. The dropping speed can be 0.3g/min to 0.5 g/min. For example, the dropping rate may be 0.4 g/min. The dropping speed is less than 0.3g/min or more than 0.5g/min, which is not favorable for the formation of the mesoporous structure, and too fast or too slow dropping speed may change the size of the pores, so that the change of the size of the pores causes non-formed mesopores.
Further, the carbon source may be at least one of glucose, sucrose and maltose. The carbon source has wide sources and low price, and can save cost compared with other carbon sources. The addition amount of the carbon source is related to the thickness of the formed amorphous carbon layer, the addition amount of the carbon source is too small, the generated amorphous carbon is thin and cannot play a role in relieving volume expansion, the addition amount of the carbon source is more, the generated amorphous carbon layer is thick, and the carbon may contribute to capacity for carbon during the first-turn charging and discharging of the battery, so that the stability and the cycle performance of the battery are not facilitated. For the above reasons, the amount of the carbon source to be added may be (0.8 to 6):1, for example, 5.2:1, and further, for example, 0.95:1, based on the mass of the transition metal salt.
Further, obtaining coke coated transition metal sulfides may include: uniformly mixing the solution containing the transition metal sulfide and a carbon source, and then carrying out hydrothermal reaction at the temperature of 160-240 ℃ for 6-24 hours. The temperature and the reaction time of the hydrothermal reaction are set so as to avoid the formation of a uniform amorphous carbon coating layer on the transition metal sulfide particles. For example, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 20 hours.
Furthermore, the calcining temperature can be 500-900 ℃, and the calcining time can be 1-3 hours. For example, the temperature of calcination may be 750 ℃ and the time of calcination may be 2 hours.
Further, obtaining the transition metal sulfide-containing solution may specifically include: adding a dispersing agent, a transition metal salt molten salt and a sulfur source into an ethylene glycol solution at a preset adding speed, stirring by a magnetic stirrer until the dispersing agent, the transition metal salt molten salt and the sulfur source are completely dissolved, placing the completely dissolved solution into a high-pressure reaction kettle, and preparing a transition metal sulfide-containing solution through a hydrothermal reaction.
And further, centrifuging and cleaning the transition metal sulfide coated by the coke, and drying the transition metal sulfide coated by the coke, repeatedly washing the transition metal sulfide solution coated by the coke, and drying the transition metal sulfide solution in a vacuum drying oven. The temperature of vacuum drying can be 60-90 ℃, and the drying time can be 10-14 hours.
Further, the inert atmosphere may be an argon atmosphere, a nitrogen atmosphere, or the like.
The invention also provides a carbon-coated mesoporous transition metal sulfide negative electrode material. In an exemplary embodiment of the carbon-coated mesoporous transition metal sulfide cathode material, the carbon-coated mesoporous transition metal sulfide cathode material may be prepared by the above method for preparing a carbon-coated mesoporous transition metal sulfide cathode material, the carbon-coated mesoporous transition metal sulfide cathode material may be formed by stacking a plurality of nanoscale primary particles, each primary particle is composed of an inner layer of transition metal sulfide and an amorphous carbon coating layer coated on the surface of the transition metal sulfide, and a mesoporous structure is formed between the plurality of primary particles. The mesopores formed between the particles are uniform mesopores.
Furthermore, the size of the mesopores can be 2 to 50 nanometers. When the pore diameter is less than 2 nanometers, the desorption of sodium ions and lithium ions is not realized; the pore diameter is larger than 50 nanometers, and the structure is collapsed when volume expansion of sulfide occurs in the charge and discharge process, so that the structure of the material is a mesoporous structure. Preferably, the size of the mesopores can be 10 nm to 40 nm, and the structure can be conveniently de-intercalated and de-intercalated by sodium ions and lithium ions, and meanwhile, the stability of the structure is ensured.
Further, the primary particles may have a spherical structure with a radial size of several tens to several hundreds of nanometers, for example, the radial size may be 20 to 300 nanometers, and further for example, may be 100 nanometers.
Further, the primary particles may have a spherical structure with a uniform size.
In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
Example 1
Step 1: 40mL of ethylene glycol solution is weighed and dispersed in 40mL of deionized water, and the mixture is stirred until the mixture is uniform, so that the uniformly mixed ethylene glycol solution is formed.
Step 2: slowly adding 0.6g of polyvinylpyrrolidone into the ethylene glycol solution obtained in the step (1), and magnetically stirring until the polyvinylpyrrolidone is completely dissolved; then 2mmol of nickel acetate tetrahydrate (C) were slowly added4H6O4Ni·4H2O) powder, and magnetically stirring until the powder is completely dissolved; then 6mmol of Na were added2S2O3·5H2And O, magnetically stirring until the solution is completely dissolved. Then the obtained solution is placed in a high-pressure reaction kettle and heated in an oven at 180 ℃ for 10 hours to carry out hydrothermal reaction, and NiS-containing solution is formed.
And step 3: and dispersing 1.5g of glucose into the obtained NiS-containing solution, stirring the solution uniformly to form a uniform mixed solution, placing the uniform mixed solution into a high-pressure reaction kettle, and heating the uniform mixed solution in a 180 ℃ oven for 10 hours to perform hydrothermal reaction to obtain the transition metal sulfide coated by the coke.
And 4, step 4: and (4) centrifuging the product obtained in the step (3), repeatedly washing, and drying in a vacuum drying oven at 60 ℃ for 10 h.
And 5: and (4) placing the product obtained in the step (4) in a tubular furnace, and calcining for 3 hours at the temperature of 600 ℃ in the Ar atmosphere to obtain the NiS/C negative electrode material.
The microstructure of the carbon-coated mesoporous transition metal sulfide NiS/C anode material prepared by the method is shown in figure 1. The NiS/C cathode material is of a uniform mesoporous spherical structure, NiS/C particles are stacked together, and uniform mesopores are formed among the particles.
Uniformly mixing NiS/C negative electrode material, conductive carbon (SP) and PVDF in NMP according to the mass ratio of 8:1:1 to obtain uniform black slurry; and the slurry was adjusted to 1.5 mg/cm2The area load of the NiS/C electrode plate is loaded on a current collector made of a copper foil material to obtain a NiS/C electrode plate; and assembling the prepared mesoporous NiS/C electrode pole piece into a lithium ion battery and measuring the electrochemical performance of the lithium ion battery.
The assembly process is as follows: NiS/C electrode piece is used as a negative electrode, 1.0M LiTFSI is dissolved in Dimethoxyethane (DME), 1,3-Dioxolane (DOL) =1:1Vol%, and LiNO is 2.0%3And as an electrolyte, a lithium sheet is used as a counter positive electrode, Celgard2325 is used as a diaphragm, and CR2016 type stainless steel is used as a battery shell to assemble the button type lithium ion battery.
And (3) electrochemical performance testing: at 25 deg.C, the charge and discharge cycle is performed at a current density of 0.1A/g between 0.1V and 3.0V, and the charge and discharge curve is shown in FIG. 2, wherein curve a represents the first charge performance curve, and curve b represents the first discharge performance curve. As shown in fig. 2, the surface discharge specific capacity and the charge specific capacity of the first (first-turn) charge-discharge curve are close to each other, and the calculated coulombic efficiency is greater than 90%, which indicates that the reversible capacity of the lithium battery is high. The cycle performance graph is shown in figure 3, the first specific discharge capacity of the lithium ion battery can reach 680mAh/g, which shows that the lithium ion battery has high specific discharge capacity. And, as shown in fig. 3, after circulating for 100 circles, the specific discharge capacity is kept above 500 mAh/g and tends to be stable, so the circulation performance is better and the service life of the battery is long.
Example 2
Step 1: 35mL of ethylene glycol solution was measured and dispersed in 45 mL of deionized water, and stirred until uniform to form a uniformly mixed ethylene glycol solution.
Step 2: slowly adding 0.5g of polyvinylpyrrolidone into the ethylene glycol solution obtained in the step 1, and magnetically stirring until the polyvinylpyrrolidone is completely dissolved; slowly adding 1.5g of cobalt chloride, magnetically stirring until the cobalt chloride is completely dissolved, then adding 0.9g of thiourea, and magnetically stirring until the cobalt chloride is completely dissolved. And then placing the obtained solution in a high-pressure reaction kettle, and heating in an oven at 230 ℃ for 20 hours to perform hydrothermal reaction to form a CoS-containing solution.
And step 3: 2.5g of sucrose is dispersed in the CoS-containing solution, stirred to be uniform to form a uniform mixed solution, then the uniform mixed solution is placed in a high-pressure reaction kettle, and heated in an oven at 240 ℃ for 24 hours to carry out hydrothermal reaction.
And 4, step 4: centrifuging the solution obtained in the step (3) to obtain a product, cleaning, placing the product in a vacuum drying oven at 90 ℃ for drying for 14h,
and 5: putting the product obtained in the step 4 into a tube furnace N2Calcining for 1h at 900 ℃ in the atmosphere to obtain the CoS/C cathode material.
The CoS/C electrode plate is prepared from the CoS/C negative electrode material according to the preparation method of the electrode plate in the example 1, and then the prepared CoS/C electrode plate is assembled into a lithium ion battery and the electrochemical performance of the lithium ion battery is measured.
The assembly process is as follows: CoS/C electrode piece is used as a negative electrode, 1.0M LiTFSI is dissolved in Dimethoxyethane (DME), 1,3-Dioxolane (DOL) =1:1Vol%, and LiNO is 2.0%3And as an electrolyte, a lithium sheet is used as a counter positive electrode, Celgard2325 is used as a diaphragm, and CR2016 type stainless steel is used as a battery shell to assemble the button type lithium ion battery.
And (3) electrochemical performance testing: when the charge and discharge cycle is carried out at 25 ℃ and the multiplying power of 0.1A/g between 0.1V and 3.0V, the first charge and discharge specific capacity can reach 620 mAh/g.
Example 3
Step 1: 60mL of ethylene glycol solution is weighed and dispersed in 20mL of deionized water, and the mixture is stirred until the mixture is uniform, so that a uniform mixed solution is formed.
Step 2: slowly adding 0.4g of polyvinylpyrrolidone into the ethylene glycol solution obtained in the step 1, and magnetically stirring until the polyvinylpyrrolidone is completely dissolved; slowly add 3g of vanadium sulfate (V)2(SO4)3) Magnetically stirring until completely dissolved, and adding 2g Na2S2O3·5H2And O, magnetically stirring until the solution is completely dissolved. Then placing the obtained solution inHeating the mixture in a high-pressure reaction kettle in a 230 ℃ oven for 12 hours to carry out hydrothermal reaction to form a solution containing nano vanadium sulfide.
And step 3: dispersing 2.5g of sucrose in the solution containing vanadium sulfide, stirring the solution uniformly to form a uniform mixed solution, placing the uniform mixed solution in a high-pressure reaction kettle, and heating the uniform mixed solution in a 240 ℃ oven for 24 hours to perform hydrothermal reaction.
And 4, step 4: centrifuging the solution obtained in the step (3) to obtain a product, drying the product in a vacuum drying oven at the temperature of 60 ℃ for 10 hours,
and 5: putting the product obtained in the step 4 into a tube furnace N2Calcining for 2 hours at 750 ℃ in atmosphere to obtain V2S3a/C negative electrode material.
V was prepared according to the method for preparing an electrode sheet in example 12S3the/C cathode material is prepared into V2S3a/C electrode pole piece. The prepared V2S3And assembling the/C electrode pole piece into a sodium-ion battery and measuring the electrochemical performance of the sodium-ion battery. The assembly process is as follows: using a flower-like shape V2S3The active material is composed of/C, acetylene black and sodium carboxymethyl cellulose (CMC), wherein the active material, the acetylene black and the sodium carboxymethyl cellulose are in a mass ratio of 80: 10: 10; mixing them according to a certain proportion, ultrasonic treating to make them uniform, coating them on the copper foil, vacuum drying, then making sheet-punching by about 1cm on sheet-punching machine2Size; with 1M NaClO4The sodium-ion battery is dissolved in Diglyme (DGM) to be used as electrolyte, a sodium sheet is used as a counter electrode, Celgard2325 is used as a diaphragm, and CR2025 type stainless steel is used as a battery shell to assemble the button type sodium-ion battery.
And (3) electrochemical performance testing: when the charge and discharge cycle is carried out at 25 ℃ and the current density of 0.1A/g is between 0.1V and 3.0V, the first charge and discharge specific capacity can reach 578 mAh/g.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a carbon-coated mesoporous transition metal sulfide negative electrode material is characterized by comprising the following steps:
mixing polyvinylpyrrolidone, a transition metal salt solution and a sulfur source, and heating until the reaction is finished to obtain a transition metal sulfide-containing solution;
uniformly mixing a transition metal sulfide-containing solution with a carbon source, and heating until the reaction is finished to obtain a transition metal sulfide coated by coke;
centrifuging, cleaning and drying the transition metal sulfide coated by the coke to obtain solid transition metal sulfide powder;
and calcining the solid transition metal sulfide powder in an inert atmosphere to obtain the carbon-coated mesoporous transition metal sulfide negative electrode material.
2. The method for preparing the carbon-coated mesoporous transition metal sulfide cathode material according to claim 1, wherein the transition metal salt is at least one of a nickel salt, a cobalt salt, a manganese salt, a vanadium salt, a molybdenum salt, a tungsten salt, a tin salt, an iron salt, a zinc salt, a copper salt and an antimony salt.
3. The method for preparing the carbon-coated mesoporous transition metal sulfide negative electrode material as claimed in claim 1, wherein the sulfur source is at least one of thiosulfate and thiourea.
4. The preparation method of the carbon-coated mesoporous transition metal sulfide negative electrode material as claimed in claim 1, 2 or 3, wherein the solution containing the transition metal sulfide is obtained by mixing polyvinylpyrrolidone, a transition metal salt solution and a sulfur source and then performing a hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 160 ℃ to 240 ℃ and the reaction time is 6 hours to 24 hours.
5. The method for preparing the carbon-coated mesoporous transition metal sulfide anode material according to claim 4, wherein obtaining the transition metal sulfide-containing solution comprises:
preparing an ethylene glycol aqueous solution;
uniformly mixing polyvinylpyrrolidone with an ethylene glycol aqueous solution, adding a transition metal salt and a sulfur source, completely dissolving, and carrying out hydrothermal reaction to obtain a transition metal-containing sulfide solution.
6. The method for preparing the carbon-coated mesoporous transition metal sulfide anode material according to claim 1, 2, 3 or 5, wherein the carbon source is at least one of glucose, sucrose and maltose.
7. The preparation method of the carbon-coated mesoporous transition metal sulfide cathode material as claimed in claim 1, 2, 3 or 5, wherein the coke-coated transition metal sulfide is obtained by a hydrothermal reaction after a transition metal sulfide-containing solution and a carbon source are uniformly mixed, wherein the temperature of the hydrothermal reaction is 160 ℃ to 240 ℃, and the reaction time is 6 hours to 24 hours.
8. The method for preparing the carbon-coated mesoporous transition metal sulfide negative electrode material as claimed in claim 1, 2, 3 or 5, wherein the calcining temperature is 500 ℃ to 900 ℃, and the calcining time is 1 hour to 3 hours.
9. The carbon-coated mesoporous transition metal sulfide anode material prepared by the method for preparing the carbon-coated mesoporous transition metal sulfide anode material according to any one of claims 1 to 8, which has a mesoporous structure formed by stacking a plurality of nanoscale primary particles, wherein the primary particles are composed of transition metal sulfide at an inner layer and an amorphous carbon coating layer coated on the surface of the transition metal sulfide.
10. The carbon-coated mesoporous transition metal sulfide negative electrode material prepared by the preparation method of the carbon-coated mesoporous transition metal sulfide negative electrode material according to any one of claims 1 to 8 or the application of the carbon-coated mesoporous transition metal sulfide negative electrode material according to claim 9 in lithium ion batteries, sodium ion batteries and lithium sulfur batteries.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113415827A (en) * | 2021-05-31 | 2021-09-21 | 中南大学 | Preparation method and application of manganese sulfide/porous carbon energy storage material |
CN114824204A (en) * | 2022-04-14 | 2022-07-29 | 中南大学 | Preparation method of carbon-coated cobalt-nickel binary transition metal sulfide negative electrode material |
CN115125575A (en) * | 2022-07-11 | 2022-09-30 | 广东工业大学 | Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst, preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108232142A (en) * | 2017-12-22 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of zinc sulphide/graphene composite material, preparation method and application |
CN110797515A (en) * | 2019-10-09 | 2020-02-14 | 天津大学 | Method for preparing three-dimensional mesoporous cobalt octasulfide nona-carbon nanofiber-sulfur lithium sulfur battery positive electrode material |
CN112018344A (en) * | 2020-07-13 | 2020-12-01 | 昆明理工大学 | Carbon-coated nickel sulfide electrode material and preparation method and application thereof |
-
2021
- 2021-01-11 CN CN202110033317.5A patent/CN112768656A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108232142A (en) * | 2017-12-22 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of zinc sulphide/graphene composite material, preparation method and application |
CN110797515A (en) * | 2019-10-09 | 2020-02-14 | 天津大学 | Method for preparing three-dimensional mesoporous cobalt octasulfide nona-carbon nanofiber-sulfur lithium sulfur battery positive electrode material |
CN112018344A (en) * | 2020-07-13 | 2020-12-01 | 昆明理工大学 | Carbon-coated nickel sulfide electrode material and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
RUIMIN SUN等: "Mesoporous NiS2 Nanospheres Anode with Pseudocapacitance for High-Rate and Long-Life Sodium-Ion Battery", 《SMALL》 * |
WEI JI等: "Nitrogen-doped carbon coating mesoporous ZnS nanospheres as high-performance anode material of sodium-ion batteries", 《MATERIALS TODAY COMMUNICATIONS》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113415827A (en) * | 2021-05-31 | 2021-09-21 | 中南大学 | Preparation method and application of manganese sulfide/porous carbon energy storage material |
CN113415827B (en) * | 2021-05-31 | 2022-05-27 | 中南大学 | Preparation method and application of manganese sulfide/porous carbon energy storage material |
CN114824204A (en) * | 2022-04-14 | 2022-07-29 | 中南大学 | Preparation method of carbon-coated cobalt-nickel binary transition metal sulfide negative electrode material |
CN115125575A (en) * | 2022-07-11 | 2022-09-30 | 广东工业大学 | Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst, preparation method and application thereof |
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