CN117878330A - Tricobalt tetraoxide-porous carbon sheet composite material, preparation method thereof and application thereof in lithium-sulfur battery - Google Patents
Tricobalt tetraoxide-porous carbon sheet composite material, preparation method thereof and application thereof in lithium-sulfur battery Download PDFInfo
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- CN117878330A CN117878330A CN202410215698.2A CN202410215698A CN117878330A CN 117878330 A CN117878330 A CN 117878330A CN 202410215698 A CN202410215698 A CN 202410215698A CN 117878330 A CN117878330 A CN 117878330A
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- porous carbon
- carbon sheet
- cobaltosic oxide
- composite material
- sulfur
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 161
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- -1 hydroxide ions Chemical class 0.000 claims description 20
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 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
- 239000006185 dispersion Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000014233 sulfur utilization Effects 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 229920001021 polysulfide Polymers 0.000 description 13
- 239000005077 polysulfide Substances 0.000 description 13
- 150000008117 polysulfides Polymers 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 8
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium sulfur batteries, and discloses a cobaltosic oxide-porous carbon sheet composite material, a preparation method thereof and application thereof in the lithium sulfur batteries, wherein the preparation method comprises the following steps: s1, dispersing sodium chloride, sodium silicate, a carbon source and a nitrogen source in water, uniformly dispersing, drying, and carbonizing to obtain a porous carbon sheet; s2, dispersing the porous carbon sheet in a cobalt source solution, and performing hydrothermal treatment after dropwise adding an alkaline solution to obtain the cobaltosic oxide-porous carbon sheet composite material. The cobaltosic oxide-porous carbon sheet composite material is synthesized by a comprehensive template method and a hydrothermal method, is designed into a sulfur host and an interlayer material and is applied to a lithium-sulfur battery, so that the oxidation-reduction reaction of sulfur is promoted, and the conductivity of a sulfur-related product is improved. The cobaltosic oxide-porous carbon sheet composite material constructed by the invention has excellent conductivity and catalytic activity, and solves the problems of poor cycling stability, low sulfur utilization rate, low coulomb efficiency and the like of a lithium-sulfur battery.
Description
Technical Field
The invention belongs to the technical field of lithium sulfur batteries, and particularly relates to a cobaltosic oxide-porous carbon sheet composite material, a preparation method thereof and application thereof in the lithium sulfur batteries, and particularly the cobaltosic oxide-porous carbon sheet composite material can be used as a diaphragm material or a positive electrode material to be applied to the lithium sulfur batteries.
Background
The lithium-sulfur battery is one of potential candidate batteries of the next generation electrochemical energy storage technology because of the advantages of high theoretical energy density, high theoretical capacity and the like. However, factors such as poor cycling stability, low sulfur utilization, low coulombic efficiency, and volume expansion during discharge, which are caused by slow redox kinetics and shuttle effects of polysulfides during cycling, limit the commercialization development of lithium sulfur batteries. For the improvement of the performance of lithium sulfur batteries, some carbon materials including porous carbon, graphene, carbon nanotubes and hybrids thereof were originally applied to physically encapsulate sulfur species and increase their conductivity. However, only weak physical adsorption exists between the nonpolar carbon material and the polar polysulfide, which is far insufficient to prevent the diffusion of polysulfide, and the shuttle effect is completely solved. While doping of heteroatoms (e.g., nitrogen, oxygen, sulfur) may provide weaker chemisorption, the interactions are not yet strong enough. In addition, some non-conductive polar inorganic substances (e.g., alumina, silica, titania) can effectively adsorb polysulfides by strong chemical interactions with polysulfides. However, recycling of polysulfides is disadvantageous because of the poor conductivity of these inorganic materials. Thus, some catalytic metals (e.g., nickel, platinum, and cobalt) and conductive compounds (e.g., ferroferric oxide, cobalt disulfide, molybdenum disulfide) that are capable of catalyzing the conversion of polysulfides are of great interest. However, the conductivity of such catalytic materials is intermediate between that of carbon materials and non-conductive polar inorganic materials, and the application of the above classes of single materials is not sufficient to completely solve the problems of poor cycle performance, low coulombic efficiency, low sulfur utilization, and the like of lithium sulfur batteries. In addition, many researches are currently focused on synthesizing various forms of carbon materials, polar materials or catalytic materials through complicated processes and expensive raw materials, thereby reducing the dissolution of polysulfides and improving the conductivity of sulfur species. In the prior art, the preparation method of the material often involves multi-step drying, washing, calcining and other treatments, wherein the calcining temperature is generally higher than 400 ℃, the energy consumption is high, and the argon-hydrogen/nitrogen-hydrogen mixed gas is also required to be matched, so that the higher cost is caused. In addition, expensive raw materials (such as cetyl trimethylammonium bromide, metal organic framework materials, etc.) are often chosen to control the formation of materials with different morphologies. These complex steps and expensive raw materials are extremely disadvantageous for industrial production and commercialization of lithium sulfur batteries. Therefore, how to combine the advantages of the above materials and to use raw materials with simpler process and lower cost to improve the performance and industrial application of lithium-sulfur batteries remains a big problem.
Disclosure of Invention
In view of the above-mentioned drawbacks or improvements of the prior art, an object of the present invention is to provide a tricobalt tetraoxide-porous carbon sheet composite material, a preparation method thereof, and an application thereof in a lithium sulfur battery, wherein the tricobalt tetraoxide-porous carbon sheet composite material is synthesized by a comprehensive template method and a hydrothermal method, and meanwhile, the tricobalt tetraoxide-porous carbon sheet composite material is designed into a sulfur host and an interlayer material to be applied to the lithium sulfur battery, so as to promote the oxidation-reduction reaction of sulfur and improve the conductivity of sulfur-related products. The cobaltosic oxide-porous carbon sheet composite material constructed by the invention has excellent conductivity and catalytic activity, and solves the problems of poor cycling stability, low sulfur utilization rate, low coulomb efficiency and the like of a lithium-sulfur battery.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a tricobalt tetraoxide-porous carbon sheet composite material, characterized by comprising the steps of:
s1, preparing a porous carbon sheet:
dispersing sodium chloride, sodium silicate, a carbon source and a nitrogen source in deionized water together, and drying after uniform dispersion; then, carbonizing the mixture obtained by drying under protective atmosphere, cooling, washing and drying the reaction product to obtain a porous carbon sheet;
s2, preparing a cobaltosic oxide-porous carbon sheet composite material:
preparing a cobalt source solution and an alkaline solution, ultrasonically stirring and dispersing the porous carbon sheet obtained in the step S1 into the cobalt source solution, and then dropwise adding the alkaline solution into the cobalt source solution to obtain a mixed solution; and then carrying out hydrothermal treatment on the mixed solution, collecting a product, washing and drying to obtain the cobaltosic oxide-porous carbon sheet composite material.
As a further preferred aspect of the present invention, in step S1,
the carbon source is selected from glucose, sucrose, citric acid and chitosan;
the nitrogen source is selected from urea, thiourea, cyanamide and dicyandiamide;
the mass ratio of the carbon source to the nitrogen source is (1-1.25): 1;
in the step S2 of the process,
the cobalt source in the cobalt source solution is selected from cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate;
the alkali in the alkaline solution is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide.
As a further preferred aspect of the present invention, in step S2, in the mixed solution, a molar ratio of cobalt ions of the cobalt source solution to hydroxide ions of the alkaline solution is 1:2 to 4:1;
the mixed solution is subjected to hydrothermal treatment, in particular to a reaction kettle, the adopted heating rate is 2 ℃/min-5 ℃/min, the hydrothermal treatment temperature is 175-185 ℃, and the hydrothermal treatment time is 6-48 hours.
In the step S1, sodium chloride, sodium silicate, a carbon source and a nitrogen source are jointly dispersed in deionized water, and are uniformly dispersed and then are subjected to drying treatment, wherein the drying is freeze-drying, the drying time is 48-72 hours, and the drying temperature is-70-50 ℃;
the carbonization treatment is carried out under the atmosphere of nitrogen or argon, the adopted heating rate is 2 ℃/min-5 ℃/min, the carbonization temperature is 700 ℃ -800 ℃, and the carbonization time is 2 hours-4 hours.
As a further preferred aspect of the present invention, in step S2, the treatment time of the ultrasonic agitation is 1 hour to 4 hours;
in the cobaltosic oxide-porous carbon sheet composite material, the mass percentage of the cobaltosic oxide is 15-60%, and the mass percentage of the porous carbon sheet is 40-85%.
According to another aspect of the invention, the invention provides a cobaltosic oxide-porous carbon sheet composite material prepared by the preparation method.
According to a further aspect of the invention, the invention provides the use of the cobalt oxide-porous carbon sheet composite material in modifying a lithium sulfur battery separator.
As a further preferred aspect of the invention, the application is in particular: mixing the cobaltosic oxide-porous carbon sheet composite material with a conductive agent and a binder, adding a solvent, uniformly dispersing, coating the mixture on a diaphragm base film, and then drying to obtain a lithium sulfur battery diaphragm modified by the cobaltosic oxide-porous carbon sheet composite material;
preferably, the conductive agent is selected from conductive carbon black, acetylene black, ketjen black and carbon nanotubes; the binder is selected from aqueous dispersion liquid of polyvinylidene fluoride, carboxymethyl cellulose and acrylonitrile multi-copolymer, and styrene butadiene rubber emulsion; the solvent is selected from N-methyl pyrrolidone and deionized water; the diaphragm base film is selected from a polypropylene film, a polyethylene film and a Celgard2325 composite diaphragm;
the tricobalt tetraoxide-porous carbon sheet composite material, the conductive agent and the binder are mixed according to the mass ratio of (50-90): (5-45).
According to a further aspect of the invention, the invention provides the use of the cobalt oxide-porous carbon sheet composite material described above in the preparation of a composite sulphur cathode material.
As a further preferred aspect of the invention, the application is in particular: dissolving sodium thiosulfate in a mixed solution of deionized water and absolute ethyl alcohol to obtain a sodium thiosulfate solution; meanwhile, adding the cobaltosic oxide-porous carbon sheet into an acid solution, stirring to obtain an acid solution containing the cobaltosic oxide-porous carbon sheet, and carrying out acid solution treatment on the carbon material; then, adding the acid solution containing the cobaltosic oxide-porous carbon sheet into the sodium thiosulfate solution, and stirring to obtain a black solution; then adding the carbon material treated by the acid solution into the black solution, continuously stirring, and then washing and drying the product to obtain the cobaltosic oxide-porous carbon sheet composite sulfur anode material;
preferably, the carbon material is selected from carbon nanotubes, graphene, acetylene black, ketjen black;
more preferably, in the cobaltosic oxide-porous carbon sheet composite sulfur positive electrode material, the mass percentage of nano sulfur particles is 20% -80%, the mass percentage of the cobaltosic oxide-porous carbon sheet is 10% -70%, and the mass percentage of the carbon material is 10% -70%.
By the above technical scheme, compared with the prior art, the invention can obtain the following
The beneficial effects are that:
(1) The cobaltosic oxide-porous carbon sheet composite material obtained based on the method provides rich catalytic active sites, is beneficial to promoting the transformation and utilization of polysulfide, improves electrochemical reaction kinetics, and meanwhile, the rich pore structure can promote the diffusion of lithium ions, so that the lithium-sulfur battery can realize stable circulation under high current.
(2) The membrane of the lithium sulfur battery modified by the cobaltosic oxide-porous carbon sheet composite material constructed by the invention has good cycle performance. In the following examples, the specific discharge capacity achieved in the first turn of example 1 was 1073.2mAh/g at a charge/discharge rate of 1C, the specific discharge capacity after 400 turns was 668.9mAh/g, the coulomb efficiency was maintained at 95.7%, the capacity attenuation rate was 0.09%, and the capacity retention rate was 62.3%. In contrast, with comparative example 1, which was a commercially available, unmodified commercial separator Celgard2325, the first round was able to achieve a specific discharge capacity of 838.9mAh/g, after 300 rounds of cycling, the specific discharge capacity remained at 389.8mAh/g, the coulomb efficiency was maintained at 70.4%, the capacity decay rate was 0.18%, and the capacity retention rate was 46.5%. Compared with the prior art, the application of the cobaltosic oxide-porous carbon sheet composite material on the diaphragm can obviously improve the cycle stability, the coulombic efficiency and the sulfur utilization rate of the lithium-sulfur battery.
(3) When the cobaltosic oxide-porous carbon sheet composite sulfur positive electrode material constructed by the invention is used for preparing the positive electrode of a lithium sulfur battery, the charge-discharge specific capacity, the cycle performance and the sulfur utilization rate of the lithium sulfur battery can be effectively improved. In the following examples, the specific discharge capacity achieved in the first turn of example 2 was 809.9mAh/g at a charge/discharge rate of 1C, the specific discharge capacity remaining after 300 turns was 469.4mAh/g, the coulomb efficiency was 98.1%, the capacity reduction rate was 0.14%, and the capacity retention rate was 58%. And under the same charge-discharge multiplying power, the discharge specific capacity which can be achieved in the first turn of comparative example 2 is 634.7mAh/g, after 300 turns of the cycle, the residual discharge specific capacity is 290.2mAh/g, the coulomb efficiency is kept at 95.4%, the capacity attenuation rate is 0.18%, the capacity retention rate is 45.7%, and the cycle performance and the coulomb efficiency are not as good as those of example 2. Compared with the prior art, the introduction of the cobaltosic oxide-porous carbon sheet composite material obviously improves the charge-discharge specific capacity and the coulombic efficiency of the lithium-sulfur battery, and is beneficial to improving the sulfur utilization rate, promoting the transformation of polysulfide and improving the cycle stability.
(4) According to the preparation method, a hydrothermal method is adopted, the hydrothermal time and the raw material proportion can be preferably controlled, and the cobaltosic oxide nano particles can be loaded on the porous carbon sheet. In the following fig. 3, for example, the cobaltosic oxide-porous carbon sheet composite material obtained in embodiment 1, in which the porous carbon sheet is loaded with nano-scale cobaltosic oxide spherical particles, can generate strong interaction with polysulfide while adhering to the electron transfer path of the carbon skeleton, can effectively inhibit the diffusion of polysulfide, and improves the sulfur utilization ratio.
Drawings
Fig. 1 is an XRD pattern of the tricobalt tetraoxide-porous carbon sheet composite material prepared in example 1 and a PDF standard card control pattern.
Fig. 2 is an SEM image of the porous carbon sheet prepared in example 1.
Fig. 3 is an SEM image of the tricobalt tetraoxide-porous carbon sheet composite material prepared in example 1.
Fig. 4 is an SEM image of the tricobalt tetraoxide-porous carbon sheet composite sulfur cathode material prepared in example 2.
Fig. 5 is a graph showing the cycle performance of the tricobalt tetraoxide-porous carbon sheet composite material prepared in example 1 and the commercial separator Celgard2325 without modification in comparative example 1 as a lithium sulfur battery separator at 1C rate, respectively.
Fig. 6 is a graph showing the cycle performance of the cobaltosic oxide-porous carbon sheet composite sulfur cathode material prepared in example 2 and the carbon nanotube-sulfur cathode material in comparative example 2 as a lithium sulfur battery cathode material at 1C rate, respectively.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides a preparation method of a cobaltosic oxide-porous carbon sheet composite material and application of the cobaltosic oxide-porous carbon sheet composite material in a lithium-sulfur battery, and the preparation method comprises the following steps:
(1) The preparation method of the porous carbon sheet comprises the following specific operations:
20g of sodium chloride, 0.3g of sodium silicate, 1.25g of glucose and 1g of urea are dissolved in 80mL of deionized water, and after complete dissolution, the solution is subjected to freeze drying treatment. And (3) placing the obtained product into a porcelain boat, placing the porcelain boat into a tubular furnace protected by argon atmosphere, heating to 700 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours for carbonization, and naturally cooling to room temperature. The product obtained above was repeatedly washed with deionized water and dried at 60 ℃ for 12 hours to obtain a porous carbon sheet.
(2) The preparation method of the cobaltosic oxide-porous carbon sheet composite material comprises the following specific operations:
1.164g of cobalt nitrate hexahydrate was dissolved in 20mL of deionized water, and after complete dissolution, 0.15g of porous carbon sheet was added and sonicated for 1 hour. 0.08g of sodium hydroxide was dissolved in 20mL of deionized water, and after complete dissolution, slowly added dropwise to the cobalt nitrate solution containing porous carbon flakes (at this time, the molar ratio of cobalt ions to hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide was 2:1). Then, the solution is transferred into a high-pressure reaction kettle, the high-pressure reaction kettle is closed, the high-pressure reaction kettle is heated to 180 ℃ at a heating rate of 2 ℃/min and is kept for 12 hours, then the high-pressure reaction kettle is naturally cooled to room temperature, and the solution after the hydrothermal reaction is centrifugally washed to be neutral (washing can be repeated for a plurality of times) and is dried at 60 ℃ for 12 hours, so that the cobaltosic oxide-porous carbon sheet composite material is prepared. At this time, the mass percentage of the tricobalt tetraoxide in the prepared tricobalt tetraoxide-porous carbon sheet was 50%, and the mass percentage of the porous carbon sheet was 50%.
(3) The lithium sulfur battery diaphragm modified by the cobaltosic oxide-porous carbon sheet composite material is prepared and specifically comprises the following steps:
80mg of the cobaltosic oxide-porous carbon sheet composite material, 10mg of conductive carbon black and 10mg of polyvinylidene fluoride are added into 40 mLN-methylpyrrolidone to be mixed, after ultrasonic dispersion, the mixture is subjected to suction filtration and coated on a Celgard2325 diaphragm, and then the mixture is placed in a vacuum oven to be dried for 12 hours at 60 ℃. Cutting the membrane coated with the material by adopting a special slicer commonly used in the prior art, wherein the diameter size is about 19mm, namely the lithium sulfur battery membrane modified by the tricobalt tetraoxide-porous carbon sheet composite material.
(4) The preparation method of the lithium sulfur battery comprises the following specific operations:
taking a carbon nano tube crosslinked hollow porous carbon sphere composite sulfur anode material (see Chinese patent application CN202311740933.X for details) obtained by earlier study of the inventor as an example, dissolving the carbon nano tube crosslinked hollow porous carbon sphere composite sulfur anode material, conductive carbon black and polyvinylidene fluoride in N-methylpyrrolidone according to a mass ratio of 7:2:1, and carrying out mechanical ball milling for 2 hours to obtain uniform slurry; coating the prepared slurry on a carbon-coated aluminum foil, and drying the carbon-coated aluminum foil in a vacuum drying oven at 60 ℃ for 12 hours; and cutting the aluminum foil coated with the material by a special slicer, wherein the diameter size is about 14mm, and the aluminum foil is the positive pole piece of the lithium-sulfur battery. And assembling the anode shell, the gasket, the prepared anode piece, a certain volume of lithium sulfur electrolyte, the lithium sulfur battery diaphragm decorated by the cobaltosic oxide-porous carbon piece composite material, the lithium piece, the gasket, the spring piece and the cathode shell into the CR2032 button battery in a closed glove box with argon as shielding gas and water-oxygen partial pressure of less than 0.1ppm in sequence. The lithium sulfur electrolyte is bistrifluoromethylLithium alkanesulfonyl imide (LiTFSI) was dissolved in a mixed solution of ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) in a volume ratio of 1:1 and 1wt% lithium nitrate was added thereto in a volume of 40. Mu.L, and the sulfur loading of the positive electrode sheet was 1.27mg/cm 2 。
Example 2
The embodiment provides a preparation method of a cobaltosic oxide-porous carbon sheet composite material and application of the cobaltosic oxide-porous carbon sheet composite material in a lithium-sulfur battery, and the preparation method comprises the following steps:
(1) The preparation method of the porous carbon sheet comprises the following specific operations:
20g of sodium chloride, 0.3g of sodium silicate, 1.25g of glucose and 1g of urea are dissolved in 80mL of deionized water, and after complete dissolution, the solution is subjected to freeze drying treatment. And (3) placing the obtained product into a porcelain boat, placing the porcelain boat into a tubular furnace protected by argon atmosphere, heating to 700 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours for carbonization, and naturally cooling to room temperature. The product obtained above was repeatedly washed with deionized water and dried at 60 ℃ for 12 hours to obtain a porous carbon sheet.
(2) The preparation method of the cobaltosic oxide-porous carbon sheet composite material comprises the following specific operations:
1.164g of cobalt nitrate hexahydrate was dissolved in 20mL of deionized water, and after complete dissolution, 0.15g of porous carbon sheet was added and sonicated for 1 hour. 0.08g of sodium hydroxide was dissolved in 20mL of deionized water, and after complete dissolution, the solution was slowly added dropwise to a cobalt nitrate solution containing porous carbon sheets (at this time, the molar ratio of cobalt ions to hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide was 2:1). And then transferring the solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, heating to 180 ℃ at a heating rate of 2 ℃/min, preserving heat for 12 hours, naturally cooling to room temperature, centrifugally cleaning the solution after the hydrothermal reaction to be neutral, and drying at 60 ℃ for 12 hours to prepare the cobaltosic oxide-porous carbon sheet composite material. At this time, the mass percentage of the tricobalt tetraoxide in the prepared tricobalt tetraoxide-porous carbon sheet was 50%, and the mass percentage of the porous carbon sheet was 50%.
(3) The preparation method of the cobaltosic oxide-porous carbon sheet composite sulfur cathode material comprises the following specific operations:
6.6g of sodium thiosulfate was dissolved in a mixed solution of 30mL of deionized water and 30mL of absolute ethanol, and 0.1g of tricobalt tetraoxide-porous carbon plate was added to a mixed solution of 3mL of concentrated sulfuric acid (98% by mass, the same applies hereinafter) and 20mL of deionized water and stirred for 2 hours to obtain a black solution. And adding 0.2g of carbon nano tube into 2mL of concentrated sulfuric acid and 20mL of deionized water, stirring for 30 minutes, adding the mixture into the black solution, continuously stirring for 6 hours, and finally repeatedly filtering and washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain the cobaltosic oxide-porous carbon sheet composite sulfur cathode material.
(4) The preparation method of the positive pole piece of the lithium sulfur battery comprises the following specific operations:
dissolving the cobaltosic oxide-porous carbon sheet composite sulfur positive electrode material, conductive carbon black and polyvinylidene fluoride in the mass ratio of 8:1:1 in N-methylpyrrolidone, and carrying out mechanical ball milling for 2 hours to obtain uniform slurry; coating the prepared slurry on a carbon-coated aluminum foil, and drying the carbon-coated aluminum foil in a vacuum drying oven at 60 ℃ for 12 hours; cutting aluminum foil coated with the material by a special slicer, wherein the diameter size is 14mm, and the aluminum foil is the positive pole piece of the lithium-sulfur battery.
(5) The preparation method of the lithium sulfur battery comprises the following specific operations:
and assembling the positive electrode shell, the gasket, the prepared positive electrode plate, a certain volume of lithium sulfur electrolyte, celgard2325 diaphragm and lithium sheet into the CR2032 button cell by sequentially taking argon as a shielding gas, and a water-oxygen partial pressure of less than 0.1ppm in a closed glove box. The lithium sulfur electrolyte is prepared by dissolving bis (trifluoromethanesulfonyl imide) lithium (LiTFSi) in a mixed solution of ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) prepared according to a volume ratio of 1:1, adding 1wt% of lithium nitrate into the mixed solution, wherein the added volume is 40 mu L, and the sulfur carrying capacity of a positive electrode plate is 1.1mg/cm 2 。
Example 3
The procedure was carried out in the same manner as in example 1, except that the molar ratio of cobalt ions and hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide in the step of producing a tricobalt tetraoxide-porous carbon sheet (i.e., step 2) was changed to 1:2, i.e., the mass of cobalt nitrate hexahydrate was changed to 0.73g, the mass of sodium hydroxide was changed to 0.2g, the holding time (i.e., the hydrothermal reaction time) was prolonged to 48 hours, and the mass of the porous carbon sheet was changed to 0.2g (at this time, the mass percentage of tricobalt tetraoxide in the produced tricobalt tetraoxide-porous carbon sheet was 50%, and the mass percentage of the porous carbon sheet was 50%).
Example 4
The procedure was carried out in substantially the same manner as in example 2, except that in the step of producing a tricobalt tetraoxide-porous carbon sheet (i.e., step 2), the molar ratio of cobalt ions and hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide was changed to 1:2, i.e., the mass of cobalt nitrate hexahydrate was changed to 0.73g, the mass of sodium hydroxide was changed to 0.2g, the holding time was prolonged to 48 hours, and the mass of the porous carbon sheet was changed to 0.2g (at this time, the mass percentage of tricobalt tetraoxide in the produced tricobalt tetraoxide-porous carbon sheet was 50%, and the mass percentage of the porous carbon sheet was 50%).
Example 5
The procedure was carried out in substantially the same manner as in example 1, except that the molar ratio of cobalt ions and hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide in the step of producing a tricobalt tetraoxide-porous carbon sheet (i.e., step 2) was changed to 4:1, i.e., the mass of cobalt nitrate hexahydrate was changed to 1.746g, the mass of sodium hydroxide was changed to 0.06g, the holding time (i.e., hydrothermal reaction time) was reduced to 6 hours, and the mass of the porous carbon sheet was changed to 0.2g (at this time, the mass percentage of tricobalt tetraoxide in the produced tricobalt tetraoxide-porous carbon sheet was 60%, and the mass percentage of the porous carbon sheet was 40%).
Example 6
The procedure was carried out in the same manner as in example 3, except that a tricobalt tetraoxide-porous carbon sheet was produced (i.e., the molar ratio of cobalt ions and hydroxide ions corresponding to cobalt nitrate hexahydrate and sodium hydroxide in step 2) was still 1:2, but the mass of cobalt nitrate hexahydrate became 0.55g, the mass of sodium hydroxide became 0.15g, and the mass of the porous carbon sheet became 0.85g (at this time, the mass percentage of tricobalt tetraoxide in the produced tricobalt tetraoxide-porous carbon sheet was 15%, and the mass percentage of the porous carbon sheet was 85%).
Example 7
The procedure was carried out in substantially the same manner as in example 1, except that in the step of producing a porous carbon sheet (i.e., step 1), glucose was changed to 1.25g, urea was changed to 1.25g, the carbonization treatment temperature was changed to 800℃and the carbonization time was changed to 2 hours.
Example 8
The procedure was carried out in the same manner as in example 1, except that in the step of preparing a tricobalt tetraoxide-porous carbon sheet composite modified lithium sulfur battery separator (i.e., step 3), tricobalt tetraoxide-porous carbon sheet composite was changed to 100mg, conductive carbon black was changed to 90mg, polyvinylidene fluoride was changed to 10mg (at this time, the mass ratio of tricobalt tetraoxide-porous carbon sheet composite to conductive agent, binder was 50:45:5), and N-methylpyrrolidone was changed to 50mL.
Example 9
The procedure was carried out in substantially the same manner as in example 1, except that in the step of preparing a tricobalt tetraoxide-porous carbon sheet composite modified lithium sulfur battery separator (i.e., step 3), tricobalt tetraoxide-porous carbon sheet composite was changed to 100mg, conductive carbon black was changed to 10mg, polyvinylidene fluoride was changed to 90mg (at this time, the mass ratio of tricobalt tetraoxide-porous carbon sheet composite to conductive agent, binder was 50:5:45), and N-methylpyrrolidone was changed to 50mL.
Comparative example 1
The procedure was carried out in the same manner as in example 1 for preparing a lithium-sulfur battery (i.e., step 4), except that the comparative separator in this case was a commercial separator Celgard2325 without modification, and the sulfur loading of the positive electrode sheet was 1.13mg/cm 2 。
Comparative example 2
The comparative example comprises the following steps:
(1) The preparation method of the carbon nano tube-sulfur cathode material comprises the following specific operations:
6.6g of sodium thiosulfate was dissolved in 30mL of absolute ethanol and 30mL of deionized water and stirred for 30 minutes, 0.3g of carbon nanotubes was added to 4mL of concentrated sulfuric acid and 20mL of deionized water, and the acid-treated carbon nanotube solution was added to the sodium thiosulfate solution and stirred for 6 hours. And finally, repeatedly washing with deionized water and drying at 60 ℃ for 12 hours to obtain the carbon nano tube-sulfur anode material.
(2) The preparation method of the positive pole piece of the lithium sulfur battery comprises the following specific operations:
dissolving the carbon nano tube-sulfur anode material, conductive carbon black and polyvinylidene fluoride in the mass ratio of 8:1:1 in N-methylpyrrolidone, and mechanically ball-milling for 2 hours to obtain uniform slurry; coating the prepared slurry on a carbon-coated aluminum foil, and drying the carbon-coated aluminum foil in a vacuum drying oven at 60 ℃ for 12 hours; and cutting the aluminum foil coated with the material by a special slicer, wherein the diameter size is about 14mm, and the aluminum foil is the positive pole piece of the lithium-sulfur battery.
(3) The preparation method of the lithium sulfur battery comprises the following specific operations:
and assembling the positive electrode shell, the gasket, the prepared positive electrode plate, a certain volume of lithium sulfur electrolyte, a Ceglard2325 diaphragm, the lithium plate, the gasket, the spring piece and the negative electrode shell into the CR2032 button cell in a closed glove box with argon as a shielding gas and water oxygen partial pressure of less than 0.1ppm in sequence. The lithium sulfur electrolyte is prepared by dissolving bis (trifluoromethanesulfonyl imide) Lithium (LiTFSI) in a mixed solution of ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) prepared according to a volume ratio of 1:1, adding 1wt% of lithium nitrate into the mixed solution, wherein the added volume is 40 mu L, and the sulfur carrying capacity of a positive electrode plate is 1.1mg/cm 2 。
FIG. 1 is an XRD pattern of the tricobalt tetraoxide-porous carbon sheet composite material prepared in the step (2) of example 1, and the diffraction peak position of the product obtained in example 1 is completely consistent with the diffraction peak of the standard card (No. PDF 78-1970) by comparing the XRD pattern with the standard card, which indicates that the product obtained in example 1 is tricobalt tetraoxide.
Fig. 2 is an SEM image of the porous carbon sheet prepared in step (1) of example 1, and it can be observed that the porous carbon sheet has a rich pore structure. Fig. 3 is an SEM image of the cobaltosic oxide-porous carbon sheet composite material prepared in the step (2) of example 1, in which the cobaltosic oxide is loaded on the porous carbon sheet in the form of quasi-spherical nano particles with good particle-particle dispersibility and no obvious agglomeration phenomenon occurs when the molar ratio of cobalt ions to hydroxyl ions is 2:1. Fig. 4 is an SEM image of the cobaltosic oxide-porous carbon sheet composite sulfur cathode material prepared in the step (3) of example 2, the nano sulfur particles generated by the solution method are uniformly supported on the cobaltosic oxide-porous carbon sheet and the carbon nanotubes, and the carbon nanotubes are wound on the cobaltosic oxide-porous carbon sheet to form a conductive frame.
Through electrochemical performance tests, fig. 5 is a graph showing the cycle performance of the cobaltosic oxide-porous carbon sheet composite material prepared in example 1 as a lithium sulfur battery functionalized membrane under a 1C charge-discharge rate, and it is known that, under the 1C charge-discharge rate, the first round of example 1 can reach a specific discharge capacity of 1073.2mAh/g, after 400 rounds of cycle, the residual specific discharge capacity is 668.9mAh/g, the coulomb efficiency is kept at 95.7%, the capacity attenuation rate is 0.09%, and the capacity retention rate is 62.3%. Under the same conditions, the discharge specific capacity which can be achieved in the first turn of the comparative example 1 is 838.9mAh/g, the residual discharge specific capacity after 300 turns of the cycle is 389.8mAh/g, the coulomb efficiency is kept at 70.4%, the capacity attenuation rate is 0.18%, and the capacity retention rate is 46.5%. Compared with the prior art, the application of the cobaltosic oxide-porous carbon sheet composite material on the diaphragm can obviously improve the cycle stability, the coulombic efficiency and the sulfur utilization rate of the lithium-sulfur battery.
Fig. 6 is a graph showing the cycle performance of the cobaltosic oxide-porous carbon sheet composite sulfur cathode material prepared in example 2 at a charge-discharge rate of 1C, and it is known that the discharge specific capacity of the first round of example 2 is 809.9mAh/g at the charge-discharge rate of 1C, the residual discharge specific capacity after 300 rounds of cycle is 469.4mAh/g, the coulomb efficiency is maintained at 98.1%, the capacity attenuation rate is 0.14%, and the capacity retention rate is 58%. And under the same charge-discharge multiplying power, the discharge specific capacity which can be achieved in the first turn of comparative example 2 is 634.7mAh/g, after 300 turns of the cycle, the residual discharge specific capacity is 290.2mAh/g, the coulomb efficiency is kept at 95.4%, the capacity attenuation rate is 0.18%, and the capacity retention rate is 45.7%. Compared with the prior art, the introduction of the cobaltosic oxide-porous carbon sheet composite material improves the charge-discharge specific capacity and coulombic efficiency of the lithium-sulfur battery, and is beneficial to improving the sulfur utilization rate, promoting the transformation of polysulfide and improving the cycle stability.
The above embodiments are merely examples, and for example, when the lithium sulfur battery separator is modified with a tricobalt tetraoxide-porous carbon sheet composite material, the separator base film may be other lithium sulfur battery separators known in the art (e.g.Commercial separators such as polypropylene films, polyethylene films, celgard2325 composite separators, etc.); the binder may also be other binders known in the art, such as aqueous dispersions of acrylonitrile copolymers (LA 133, LA 132) and the like; other conductive agents known in the art can be used as the conductive agent; further, the mass ratio of the tricobalt tetraoxide-porous carbon sheet, the conductive agent and the adhesive can be flexibly adjusted according to practical situations (for example, the mass percentage of the tricobalt tetraoxide-porous carbon sheet can be 50% -90%, the mass percentage of the conductive agent can be 5% -45%, and the mass percentage of the adhesive can be 5% -45%). In addition, the sulfur carrying amount in the above embodiment can be flexibly adjusted, for example, 1.0mg/cm 2 ～1.5mg/cm 2 Other values within the interval. The mass ratio of the cobaltosic oxide to the porous carbon sheet in the cobaltosic oxide-porous carbon sheet can be flexibly adjusted according to actual needs, and the dosage of the cobaltosic oxide, the sodium hydroxide and the porous carbon sheet in the step (step 2) of preparing the cobaltosic oxide-porous carbon sheet (embodiment 1) can be controlled, and the quality of the carbon sheet in a system before and after the hydrothermal reaction is not changed in the hydrothermal reaction process of the step, and only the amount of the cobaltosic oxide generated by a cobalt source and an alkali source is required to be regulated.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the cobaltosic oxide-porous carbon sheet composite material is characterized by comprising the following steps of:
s1, preparing a porous carbon sheet:
dispersing sodium chloride, sodium silicate, a carbon source and a nitrogen source in deionized water together, and drying after uniform dispersion; then, carbonizing the mixture obtained by drying under protective atmosphere, cooling, washing and drying the reaction product to obtain a porous carbon sheet;
s2, preparing a cobaltosic oxide-porous carbon sheet composite material:
preparing a cobalt source solution and an alkaline solution, ultrasonically stirring and dispersing the porous carbon sheet obtained in the step S1 into the cobalt source solution, and then dropwise adding the alkaline solution into the cobalt source solution to obtain a mixed solution; and then carrying out hydrothermal treatment on the mixed solution, collecting a product, washing and drying to obtain the cobaltosic oxide-porous carbon sheet composite material.
2. The process according to claim 1, wherein in step S1,
the carbon source is selected from glucose, sucrose, citric acid and chitosan;
the nitrogen source is selected from urea, thiourea, cyanamide and dicyandiamide;
the mass ratio of the carbon source to the nitrogen source is (1-1.25): 1;
in the step S2 of the process,
the cobalt source in the cobalt source solution is selected from cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate;
the alkali in the alkaline solution is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide.
3. The preparation method according to claim 1, wherein in the step S2, a molar ratio of cobalt ions of the cobalt source solution to hydroxide ions of the alkaline solution is 1:2 to 4:1;
the mixed solution is subjected to hydrothermal treatment, in particular to a reaction kettle, the adopted heating rate is 2 ℃/min-5 ℃/min, the hydrothermal treatment temperature is 175-185 ℃, and the hydrothermal treatment time is 6-48 hours.
4. The preparation method of claim 1, wherein in the step S1, sodium chloride, sodium silicate, a carbon source and a nitrogen source are jointly dispersed in deionized water, and drying treatment is carried out after uniform dispersion, wherein the drying is freeze drying, the drying time is 48-72 hours, and the drying temperature is-70-50 ℃;
the carbonization treatment is carried out under the atmosphere of nitrogen or argon, the adopted heating rate is 2 ℃/min-5 ℃/min, the carbonization temperature is 700 ℃ -800 ℃, and the carbonization time is 2 hours-4 hours.
5. The method of claim 1, wherein in step S2, the ultrasonic agitation is performed for a period of time ranging from 1 hour to 4 hours;
in the cobaltosic oxide-porous carbon sheet composite material, the mass percentage of the cobaltosic oxide is 15-60%, and the mass percentage of the porous carbon sheet is 40-85%.
6. A tricobalt tetroxide-porous carbon sheet composite material prepared by the preparation method according to any one of claims 1-5.
7. The use of the tricobalt tetraoxide-porous carbon sheet composite material according to claim 6 for modifying a lithium sulfur battery separator.
8. The application according to claim 7, characterized in that it is in particular: mixing the cobaltosic oxide-porous carbon sheet composite material with a conductive agent and a binder, adding a solvent, uniformly dispersing, coating the mixture on a diaphragm base film, and then drying to obtain a lithium sulfur battery diaphragm modified by the cobaltosic oxide-porous carbon sheet composite material;
preferably, the conductive agent is selected from conductive carbon black, acetylene black, ketjen black and carbon nanotubes; the binder is selected from aqueous dispersion liquid of polyvinylidene fluoride, carboxymethyl cellulose and acrylonitrile multi-copolymer, and styrene butadiene rubber emulsion; the solvent is selected from N-methyl pyrrolidone and deionized water; the diaphragm base film is selected from a polypropylene film, a polyethylene film and a Celgard2325 composite diaphragm;
the tricobalt tetraoxide-porous carbon sheet composite material, the conductive agent and the binder are mixed according to the mass ratio of (50-90): (5-45).
9. The use of the tricobalt tetraoxide-porous carbon sheet composite material according to claim 6 for preparing a composite sulfur cathode material.
10. The application according to claim 9, characterized in that it is in particular: dissolving sodium thiosulfate in a mixed solution of deionized water and absolute ethyl alcohol to obtain a sodium thiosulfate solution; meanwhile, adding the cobaltosic oxide-porous carbon sheet into an acid solution, stirring to obtain an acid solution containing the cobaltosic oxide-porous carbon sheet, and carrying out acid solution treatment on the carbon material; then, adding the acid solution containing the cobaltosic oxide-porous carbon sheet into the sodium thiosulfate solution, and stirring to obtain a black solution; then adding the carbon material treated by the acid solution into the black solution, continuously stirring, and then washing and drying the product to obtain the cobaltosic oxide-porous carbon sheet composite sulfur anode material;
preferably, the carbon material is selected from carbon nanotubes, graphene, acetylene black, ketjen black;
more preferably, in the cobaltosic oxide-porous carbon sheet composite sulfur positive electrode material, the mass percentage of nano sulfur particles is 20% -80%, the mass percentage of the cobaltosic oxide-porous carbon sheet is 10% -70%, and the mass percentage of the carbon material is 10% -70%.
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