CN109616611A - A kind of lithium-sulfur family mixed energy storage system - Google Patents
A kind of lithium-sulfur family mixed energy storage system Download PDFInfo
- Publication number
- CN109616611A CN109616611A CN201811244603.0A CN201811244603A CN109616611A CN 109616611 A CN109616611 A CN 109616611A CN 201811244603 A CN201811244603 A CN 201811244603A CN 109616611 A CN109616611 A CN 109616611A
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- Prior art keywords
- sulfur family
- lithium
- mixed
- anode
- storage system
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004146 energy storage Methods 0.000 title claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 113
- 239000011593 sulfur Substances 0.000 claims abstract description 113
- 239000011149 active material Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000006258 conductive agent Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 84
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 34
- 229910002804 graphite Inorganic materials 0.000 claims description 33
- 239000010439 graphite Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000006245 Carbon black Super-P Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
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- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 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 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims 2
- JVXWULXGOLZJEG-UHFFFAOYSA-N [As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[Li] Chemical compound [As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[As](=O)(O)(O)F.[Li] JVXWULXGOLZJEG-UHFFFAOYSA-N 0.000 claims 1
- NQXPWHDPIJFXOU-UHFFFAOYSA-N imino-bis(trifluoromethyl)-$l^{4}-sulfane Chemical compound FC(F)(F)S(=N)C(F)(F)F NQXPWHDPIJFXOU-UHFFFAOYSA-N 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- JNYLMODTPLSLIF-UHFFFAOYSA-N 6-(trifluoromethyl)pyridine-3-carboxylic acid Chemical group OC(=O)C1=CC=C(C(F)(F)F)N=C1 JNYLMODTPLSLIF-UHFFFAOYSA-N 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- UBMXMUDVGQEANW-UHFFFAOYSA-N 1,1,1,2,3,3,4,4-octafluoro-4-methoxy-2-(trifluoromethyl)butane Chemical compound COC(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F UBMXMUDVGQEANW-UHFFFAOYSA-N 0.000 description 1
- WMVAEJWSRBISBP-UHFFFAOYSA-N 1,1,1,2,3,3,4,4-octafluoro-4-propoxy-2-(trifluoromethyl)butane Chemical compound CCCOC(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F WMVAEJWSRBISBP-UHFFFAOYSA-N 0.000 description 1
- ROPCAGPDGFDJFJ-UHFFFAOYSA-N 1,1,2,8,8,8-hexafluoro-1-propoxyoctane Chemical compound C(CC)OC(C(CCCCCC(F)(F)F)F)(F)F ROPCAGPDGFDJFJ-UHFFFAOYSA-N 0.000 description 1
- YQHAJBWBAWASHP-UHFFFAOYSA-N 1,1-difluoro-6-methoxyhexane Chemical compound FC(F)CCCCCOC YQHAJBWBAWASHP-UHFFFAOYSA-N 0.000 description 1
- RDFFIWJXENUUIA-UHFFFAOYSA-N 1,1-difluoro-6-propoxyhexane Chemical compound C(CC)OCCCCCC(F)F RDFFIWJXENUUIA-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- GTQXEQRIVGXSAE-UHFFFAOYSA-N 1-methoxyheptane Chemical compound CCCCCCCOC GTQXEQRIVGXSAE-UHFFFAOYSA-N 0.000 description 1
- DOYXDCAHTUMXDF-UHFFFAOYSA-N 1-propoxyheptane Chemical compound CCCCCCCOCCC DOYXDCAHTUMXDF-UHFFFAOYSA-N 0.000 description 1
- VCRNFKKHEIEHCS-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;methoxymethane Chemical group COC.OCCOCCOCCOCCO VCRNFKKHEIEHCS-UHFFFAOYSA-N 0.000 description 1
- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 1
- WSBUFESJCQLHGZ-UHFFFAOYSA-N 2-[difluoro(propoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound CCCOC(F)(F)C(F)(C(F)(F)F)C(F)(F)F WSBUFESJCQLHGZ-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- MQXWORUJOLUJJV-UHFFFAOYSA-N COC(C(CCCCCC(F)(F)F)F)(F)F Chemical compound COC(C(CCCCCC(F)(F)F)F)(F)F MQXWORUJOLUJJV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YCLCFZRBVJIBMF-UHFFFAOYSA-N [Li].FC(F)(F)S(=N)C(F)(F)F Chemical compound [Li].FC(F)(F)S(=N)C(F)(F)F YCLCFZRBVJIBMF-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical group COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 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
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium-sulfur family mixed energy storage systems, belong to electrochemical energy technical field.Energy-storage system of the present invention, by mixing sulfur family anode, prelithiation cathode, electrolyte and diaphragm composition, wherein mixing sulfur family anode is by mixed active material, conductive agent I, binder I is uniformly mixed and forms the compound sulfur family anode of formation, electrolyte is lithium-sulfur family battery electrolytic solution, diaphragm is lithium battery diaphragm, wherein mixing sulfur family anode is by mixed active material, conductive agent I, binder I, which is uniformly mixed, to be obtained mixture A and is by mixed active material by the compound sulfur family anode of mixture A compression moulding formation or mixing sulfur family anode, conductive agent I, binder I, which is uniformly mixed, to be obtained mixture B and mixture B is coated to the compound sulfur family anode formed on collector I.When energy-storage system of the present invention works, while the battery behavior of the capacitance behavior and sulfur family electrochemical redox of anion adsorption desorption occurs, there is high energy density and power density.
Description
Technical field
The present invention relates to a kind of lithium-sulfur family mixed energy storage systems, belong to electrochemical energy technical field.
Background technique
Currently, facing mankind resource exhaustion, serious environmental pollution and the weather as caused by fossil energy use change
The problems such as change.In order to solve these problems, renewable, the sustainable energy system of Development of Novel are a kind of effective technology hands
Section.For example, in recent decades, the use of solar energy, tide energy and wind energy has increased, and the electricity of low carbon dioxide emission amount
Motor-car is always in Popularization And Development.Therefore, in order to efficiently use renewable energy, exploitation high-performance, safety, cheap and environment are friendly
Good energy conversion and storage system are imperative.It is preferable to lithium ion batteries and super electricity for development in these energy-storage systems
Container.Lithium ion battery is the common electrochemical appliance for storing electric energy.However, although lithium ion battery achieves commercially
Success, but they be unable to satisfy efficient storage equipment of electric tool, electric car and renewable energy etc. application it is required
High power requirements.In contrast, supercapacitor goes back table other than providing energy density more higher than traditional dielectric capacitor
Reveal the prospect applied to powerful system, because they can provide power density more higher than battery moment.However, super
The energy density of capacitor is still insufficient for needing the new application of high-energy and high power density.
In order to overcome these disadvantages, concentrating on electrode material to the research of lithium ion battery improves, for example, using silicium cathode
And lithium-rich anode.However, there are several defects for these materials itself, including low first circle coulombic efficiency, unsatisfactory times
Rate performance, the cycle life of difference, the thermal characteristics of difference and apparent voltage attenuation.In fact, it has proved that substituting battery system, example
Such as lithium-air battery, lithium-sulfur cell and sodium/Magnesium ion battery, in terms of energy/power density, safety and cost better than lithium from
Sub- battery.However, there is also respective disadvantages for these systems.Therefore, in order to solve these problems, it is recently proposed a new class of
Asymmetric energy storage system combines the high rate capability of supercapacitor and the high-energy density of lithium ion battery.This
A little systems include two distinct types of electrode material, the i.e. redox lithium ion battery material of faraday and supercapacitor
Porous carbon materials.So far, it has been reported that two kinds of key methods realize this hybrid system, including use and have electricity
The fake capacitance metal oxide of capacitive carbon electrode, and including lithium ion insertion/deintercalation in electrode body and in active carbon table
Anion-adsorption/desorption anode on face.The second class hybrid system is referred to as lithium-ion capacitor.Although being based on lithium doping
The lithium-ion capacitor of Carbon anode and the anode based on active carbon shows operating voltage more higher than supercapacitor and energy
Density, but cannot achieve the balance between the dynamics of two electrodes.
Summary of the invention
Asymmetric energy storage system in the prior art there are aiming at the problem that, the present invention provides a kind of lithium-sulfur family mixing
Energy-storage system, the present invention in lithium-sulfur family mixed energy storage system have high unit area active material load capacity, high energy
Metric density and power density and excellent cycle performance.
A kind of lithium-sulfur family mixed energy storage system is made of mixing sulfur family anode, prelithiation cathode, electrolyte and diaphragm,
Middle mixing sulfur family anode is to be uniformly mixed mixed active material, conductive agent I, binder I and form the compound sulfur family of formation just
Pole, electrolyte are lithium-sulfur family battery electrolytic solution, and diaphragm is lithium battery diaphragm.
The mixing sulfur family anode is to be uniformly mixed mixed active material, conductive agent I, binder I to obtain mixture A simultaneously
The compound sulfur family anode or mixing sulfur family anode that mixture A compression moulding is formed are by mixed active material, conductive agent I, glue
Knot agent I, which is uniformly mixed, to be obtained mixture B and mixture B is coated to the compound sulfur family anode formed on collector I.
Further, the mixed active material includes sulfur family simple substance and capacitive character porous carbon, is calculated in mass percent, mixing
Mixed active material accounts for 80 ~ 90%, conductive agent I and accounts for 5 ~ 10% in object A or mixture B, remaining is binder I；Mixed active material
Load capacity be 5 ~ 16mgcm-2。
Further, the capacitive character porous carbon is active carbon, mesoporous carbon, microporous carbon, one or more, the sulfur family of graphene
Simple substance be sulphur, selenium, tellurium it is one or more；It is calculated in mass percent, sulfur family simple substance accounts for 5 ~ 20% in mixed active material.
Further, the mixed active material the preparation method comprises the following steps: by sulfur family simple substance and capacitive character porous carbon ground and mixed
Uniformly, 6 ~ 12h of constant temperature processing keeps sulfur family simple substance evenly dispersed extremely under conditions of being subsequently placed in sulfur family simple substance fusion point temperature or more
In the duct of capacitive character porous carbon.
The conductive agent I is conductive carbon black, Super-P, acetylene black, Ketjen black, electrically conductive graphite, graphene, carbon nanotube
It is one or more, binder I be polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC),
Polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR), polyoxyethylene (PEO) it is one or more.
The collector I is one kind of aluminium foil, stainless (steel) wire, carbon paper.
The prelithiation cathode is the prelithiation cathode that graphite cathode is compressed on the formation of lithium an- ode surface, lithium-sulfur family
The graphite cathode face face mixing sulfur family anode of prelithiation cathode in mixed energy storage system；Graphite cathode is by graphite, conductive agent
II, binder II is uniformly mixed the composite graphite negative electrode or graphite cathode for obtaining mixture C and forming mixture C compression moulding
For graphite, conductive agent II, binder II to be uniformly mixed and obtain mixture D and mixture D is coated on collector II to be formed
Composite graphite negative electrode.
It being calculated in mass percent, graphite accounts for 80 ~ 95% in the mixture C or mixture D, and conductive agent accounts for 2 ~ 10%, remaining
For binder；Conductive agent II is conductive carbon black, Super-P, acetylene black, Ketjen black, electrically conductive graphite, graphene, carbon nanotube
It is one or more, binder II be polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC),
Polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR), polyoxyethylene (PEO) it is one or more, collector II be aluminium foil, stainless steel
One kind of net, carbon paper.
The lithium-sulfur family battery electrolytic solution includes electrolytic salt, organic solvent and lithium-sulfur family battery additive, electricity
Solution matter salt is lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate
(LiClO4), trifluoromethanesulfonic acid lithium (CF3SO3Li), bis- (trifluoromethyl) sulfimide lithium (LiN (SO2CF3)2) one kind or more
Kind；Organic solvent is that chain-like alkyl esters, chain phosphotriester, nitrile solvents, fluorine solvent or molecular formula are R (CH2CH2O)n-
The polyether class of R', wherein n=1-6, R are methyl or ethyl, and R' is methyl or ethyl；The dielectric constant of organic solvent is not less than
30；Lithium battery diaphragm is PP film, PE film or PP/PE/PP trilamellar membrane.
The chain-like alkyl esters can be methyl propionate etc., and chain phosphotriester can be trimethyl phosphate etc., nitrile
Solvent can be 3- methoxypropionitrile etc.；
Preferably, fluorine solvent is (perfluoroalkyl) alkyl ether of different (perfluoroalkyl) alkyl ether and/or linear chain structure, different (complete
Fluoroalkyl) alkyl ether can be H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3Or H (CF2)2OCH2CF3、H(CF2)2CH2O
(CF2)2H；(perfluoroalkyl) alkyl ether of linear chain structure can be 2- trifluoromethyl hexafluoro propyl methyl ether, 2- trifluoromethyl hexafluoro
Propyl ether, 2- trifluoromethyl hexafluoro propyl propyl ether, 3- trifluoromethyl octafluoro butyl methyl ether, 3- trifluoromethyl octafluoro butyl second
Ether, 3- trifluoromethyl octafluoro butyl propyl ether, ten fluorine amyl group methyl ether of 4- trifluoromethyl, ten fluorine amyl group ether of 4- trifluoromethyl, 4- tri-
Ten fluorine amyl group propyl ether of methyl fluoride, ten difluoro hexyl methyl ether of 5- trifluoromethyl, ten difluoro hexyl ether of 5- trifluoromethyl, 5- fluoroform
Ten difluoro hexyl propyl ether of base, ten tetrafluoro heptyl methyl ether of 6- trifluoromethyl, ten tetrafluoro heptyl ether of 6- trifluoromethyl, 6- trifluoromethyl
Ten tetrafluoro heptyl propyl ether, ten hexafluoro octyl methyl ether of 7- trifluoromethyl, ten hexafluoro octyl ether of 7- trifluoromethyl or 7- trifluoromethyl
Ten hexafluoro octyl propyl ether.
Preferably, molecular formula is R (CH2CH2O)nThe polyether class of-R' is dimethyl ether tetraethylene glycol (TEGDME), glycol dinitrate
Ether (DME) or 1,3- dioxolane (DOL)；
Organic solvent can also be the branched chain type compound solvent with ehter bond, such as dendrimer solvent；
To promote lithium-sulfur family hybrid energy-storing battery performance, lithium-sulfur family hybrid energy-storing battery needs first to carry out charge and discharge activation, preceding
When phase carries out several cycle periods, the charge and discharge for first carrying out smaller current density is electro-active, then carries out larger current density charge and discharge
The charge and discharge activation procedure of test.
Beneficial effects of the present invention:
(1) lithium of the present invention-sulfur family mixed energy storage system makees positive, prelithiation graphite electrode by sulfur family mixed electrode and makees cathode, electricity
Solution liquid and diaphragm are assembled into battery, belong to asymmetric energy storage device, due to the faraday's reaction with sulfur family active material,
High capacity may be implemented, simultaneously as the non-faraday with capacitive character carbon is reacted, high magnification may be implemented；Therefore, of the invention
Lithium-sulfur family mixed energy storage system experienced non-faraday reaction and faraday's reaction, thus provide it is higher than supercapacitor
Energy density and power density more higher than lithium ion battery；
(2) electrolyte between lithium of the present invention-sulfur family mixed energy storage system positive and negative anodes, which is mainly played through conducting lithium ions, passes
The effect of transmission of electricity lotus.Electrolyte and electrode have good wellability, and electrolyte lithium salt has good dissolubility and ion-conductance
Conductance makes battery have preferable operating temperature, specific energy, cycle efficieny, security performance；Diaphragm is active by the positive and negative anodes of battery
Substance separates, and avoids any electron stream of positive and negative interpolar from directly passing through, avoids battery short circuit；Lithium ion battery separator, ion circulation
Out-of-date resistance is small；
(3) lithium of the present invention-sulfur family mixed energy storage system utilizes the oxidation between prelithiation graphite cathode and mixing sulfur family anode also
The selective sulfur family active matter of original reaction, Anion-adsorption/desorption on the porous carbon surface of capacitive character and capacitive character porous carbon
Matter infiltration, can overcome the porous carbon supercapacitor of conventional capacitive and lithium-sulfur family battery defect, realize high capacity, good
Multiplying power property and cycle efficieny.
Detailed description of the invention
Fig. 1 is that the SEM of 1 AC-Se-10 mixed active material of embodiment schemes；
Fig. 2 is the charging and discharging curve figure of 1 AC-Se-10 hybrid energy-storing battery of embodiment；
Fig. 3 is the circulation figure of 1 AC-Se-10 hybrid energy-storing battery of embodiment；
Fig. 4 is the high rate performance figure of 1 AC-Se-10 hybrid energy-storing battery of embodiment；
The SEM that Fig. 5 is 1 AC of comparative example schemes；
Fig. 6 is the charging and discharging curve figure of the asymmetric pure energy battery of 1 AC of comparative example；
Fig. 7 is the circulation figure of the asymmetric pure energy battery of 1 AC of comparative example；
Fig. 8 is lithium-sulfur family mixed energy storage system assembling schematic diagram.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1: a kind of lithium-sulfur family mixed energy storage system, by mixing sulfur family anode, prelithiation cathode, electrolyte and every
Film composition, wherein mixing sulfur family anode is to be uniformly mixed mixed active material, conductive agent I, binder I and form answering for formation
Sulfur family anode is closed, electrolyte is lithium-sulfur family battery electrolytic solution (two (trifluoromethane sulfonic acid) imine lithiums (LiTFSI)-of 1M
The volume ratio of DOL/DME(DOL/DME is 1:1), the LiNO for being 1% containing mass concentration3), diaphragm is lithium battery diaphragm (three
Layer porous septum (PP/PE/PP))；
Mixing sulfur family anode is to be uniformly mixed mixed active material, conductive agent I (Super-P conductive carbon), binder I (PTFE)
It obtains mixture B and mixture B is coated to the compound sulfur family anode formed on collector I；Concrete operation step are as follows: will mix
Active material, conductive agent I (Super-P conductive carbon) ground and mixed uniformly obtain mixture I；Binder I (PTFE) is dissolved in
Bonding agent dispersing liquid I is obtained in deionized water, and then mixture I, bonding agent dispersing liquid I and deionized water are uniformly mixed and obtained
Active material powdery pulp I；Active material powdery pulp I is passed through into electricity of the blade coating on stainless steel collector, after coating
Pole piece dry deionized water that removes for 24 hours in the vacuum drying oven that temperature is 60 DEG C in pole obtains sulfur family blended anode；Wherein mixing is lived
Property substance include sulfur family simple substance (selenium powder) and capacitive character porous carbon (active carbon), be calculated in mass percent, in mixture B mix live
Property substance account for 80%, conductive agent I and account for 10%, remaining is binder I；The load capacity of mixed active material is 10.50mgcm-2；
Mixed active material the preparation method comprises the following steps: sulfur family simple substance (selenium powder) and capacitive character porous carbon (active carbon) ground and mixed is equal
It is even, it is calculated in mass percent, sulfur family simple substance accounts for 10% in mixed active material；It is subsequently placed in sulfur family simple substance (selenium) fusion point temperature
Constant temperature processing 6h makes the evenly dispersed hole to capacitive character porous carbon (active carbon) of sulfur family simple substance (selenium) under conditions of (260 DEG C) above
In road, it is labeled as AC-Se-10；The SEM figure of AC-Se-10 mixed active material is as shown in Figure 1；
Prelithiation cathode is the prelithiation cathode that graphite cathode is compressed on the formation of lithium an- ode surface, lithium-sulfur family hybrid energy-storing
The graphite cathode face face mixing sulfur family anode of prelithiation cathode in system；Graphite cathode is by graphite, II (Super- of conductive agent
P conductive carbon), binder II (PTFE) be uniformly mixed answering of obtaining that mixture D and be coated to mixture D formed on collector II
Close graphite cathode, concrete operation step are as follows: uniformly mixed graphite, conductive agent II (Super-P conductive carbon) ground and mixed
Object II；Binder I (PTFE) is dissolved in deionized water and obtains bonding agent dispersing liquid II then for mixture II, binder point
Dispersion liquid II and deionized water, which are uniformly mixed, obtains active material powdery pulp II, by active material powdery pulp II by scraping cutter painting
For cloth on stainless steel collector, the electrode plates after coating remove deionization in temperature for 24 h dry in 60 DEG C of vacuum drying oven
Water obtains graphite cathode；It is calculated in mass percent, graphite accounts for 90% in mixture D, and conductive agent II accounts for 5%, remaining is binder
II (PTFE)；
Lithium-sulfur family hybrid energy-storing battery preparation: sulfur family anode, prelithiation cathode, lithium-sulfur family battery electrolytic solution (1M will be mixed
Two (trifluoromethane sulfonic acid) imine lithium (LiTFSI)-DOL/DME(1/1 volume ratios), 1% LiNO3), (three layers of lithium battery diaphragm
Porous septum (PP/PE/PP)) composition button cell (see figure 8), i.e., in the glove box of argon atmosphere, just according to sulfur family mixing
Pole, three layers of porous septum (PP/PE/PP), prelithiation cathode (graphite cathode face sulfur family blended anode) laminated structure, be added
Electrolyte (two (trifluoromethane sulfonic acid) imine lithium (LiTFSI)-DOL/DME(1/1 volume ratios of 1M), 1% LiNO3) be assembled into
Button cell, and in battery test system test battery performance, charge and discharge blanking voltage be the V of 1.5 V ~ 3.8, charge and discharge
Current density is 0.50 mA cm-2；Battery charging and discharging curve and cycle characteristics are shown in that (AC-Se-10 hybrid energy-storing battery fills Fig. 2
Discharge curve), Fig. 3 (the circulation figure of AC-Se-10 hybrid energy-storing battery), Fig. 4 (multiplying power of AC-Se-10 hybrid energy-storing battery
Performance map).
Comparative example 1: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the sulfur family mixed active material in sulfur family blended anode is only active carbon；The SEM that Fig. 5 is AC schemes；
The performance of battery is tested in battery test system, charge and discharge blanking voltage is the V of 1.5 V ~ 3.8, charging and discharging currents density
For 0.50 mA cm-2；Battery charging and discharging curve and cycle characteristics see Fig. 6 (AC it is asymmetric it is pure can battery charging and discharging curve figure),
Fig. 7 (the circulation figure of the asymmetric pure energy battery of AC)；
As can be seen that the pattern of active carbon AC is almost unchanged, explanation before and after mixing sulfur family simple substance (selenium powder) from Fig. 1 and Fig. 5
Sulfur family simple substance (selenium powder) in embodiment 1 fully enters in the hole AC, conducive to the fixation of Se；Comparison from Fig. 2,3 and Fig. 6,7 can be with
Find out, the specific capacity of AC-Se-10 hybrid energy-storing battery is much higher than AC asymmetry energy-storage battery, this is because sulfur family simple substance (selenium
Powder) capacity is improved, from Fig. 4 (the high rate performance figure of AC-Se-10 hybrid energy-storing battery) it can be seen that AC-Se-10 hybrid energy-storing
Battery has preferable high rate performance.
Embodiment 2: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the unit area load capacity of the sulfur family mixed active material in sulfur family blended anode is 5.0 mgcm-2。
Embodiment 3: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the unit area load capacity of the sulfur family mixed active material in sulfur family blended anode is 7.0 mgcm-2。
Embodiment 4: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the unit area load capacity of the sulfur family mixed active material in sulfur family blended anode is 9.0 mgcm-2。
Embodiment 5: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the unit area load capacity of the sulfur family mixed active material in sulfur family blended anode is 13.0 mgcm-2。
Embodiment 6: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: the unit area load capacity of the sulfur family mixed active material in sulfur family blended anode is 16.0 mgcm-2；
The lithium of embodiment 2 ~ 6-sulfur family hybrid energy-storing battery tests the performance of battery, charge and discharge cut-off electricity in battery test system
Pressure is the V of 1.5 V ~ 3.8, and charging and discharging currents density is 0.50 mA cm-2；From charging and discharging curve figure and circulation figure it is found that sulphur unit
Area load amount is less than 11.0 mg cm-2When, capacity retention ratio of the battery after 100 circulations is 80% or more；Sulphur unit plane
Product load capacity is greater than 11.0 mg cm-2When, since resistance increases, specific capacity and cycle characteristics slightly reduce battery.
Embodiment 7: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: being calculated in mass percent, sulfur family simple substance (selenium powder) accounts in the sulfur family mixed active material of sulfur family blended anode
5%。
Embodiment 8: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery is made and is evaluated,
Difference is: being calculated in mass percent, sulfur family simple substance (selenium powder) accounts for 15% in the sulfur family mixed active material of sulfur family blended anode.
Embodiment 9: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: being calculated in mass percent, sulfur family simple substance (selenium powder) accounts in the sulfur family mixed active material of sulfur family blended anode
20%。
Embodiment 10: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: sulfur family simple substance is sulphur in the sulfur family mixed active material of sulfur family blended anode, is calculated in mass percent, sulphur
Sulfur family simple substance (sulphur powder) accounts for 5% in the sulfur family mixed active material of race's blended anode.
Embodiment 11: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: sulfur family simple substance is sulphur in the sulfur family mixed active material of sulfur family blended anode, is calculated in mass percent, sulphur
Sulfur family simple substance (sulphur powder) accounts for 10% in the sulfur family mixed active material of race's blended anode.
Embodiment 12: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: sulfur family simple substance is sulphur in the sulfur family mixed active material of sulfur family blended anode, is calculated in mass percent, sulphur
Sulfur family simple substance (sulphur powder) accounts for 15% in the sulfur family mixed active material of race's blended anode.
Embodiment 13: condition preparation sulfur family blended anode and prelithiation cathode similarly to Example 1, and battery progress is made
Evaluation, difference are: sulfur family simple substance is sulphur in the sulfur family mixed active material of sulfur family blended anode, is calculated in mass percent, sulphur
Sulfur family simple substance (sulphur powder) accounts for 20% in the sulfur family mixed active material of race's blended anode.
Claims (10)
1. a kind of lithium-sulfur family mixed energy storage system, it is characterised in that: by mixing sulfur family anode, prelithiation cathode, electrolyte and every
Film composition, wherein mixing sulfur family anode is to be uniformly mixed mixed active material, conductive agent I, binder I and form answering for formation
Sulfur family anode is closed, electrolyte is lithium-sulfur family battery electrolytic solution, and diaphragm is lithium battery diaphragm.
2. lithium-sulfur family mixed energy storage system according to claim 1, it is characterised in that: mixing sulfur family anode is that will mix work
Property substance, conductive agent I, binder I be uniformly mixed obtain mixture A and by mixture A compression moulding formed compound sulfur family just
Pole or mixing sulfur family anode are to be uniformly mixed mixed active material, conductive agent I, binder I to obtain mixture B and by mixture
B is coated to the compound sulfur family anode formed on collector I.
3. lithium-sulfur family mixed energy storage system according to claim 2, it is characterised in that: mixed active material includes sulfur family list
Matter and capacitive character porous carbon, are calculated in mass percent, and mixed active material accounts for 80 ~ 90%, conductive agent in mixture A or mixture B
I accounts for 5 ~ 10%, remaining is binder I；The load capacity of mixed active material is 5 ~ 16mgcm-2。
4. lithium-sulfur family mixed energy storage system according to claim 3, it is characterised in that: capacitive character porous carbon is active carbon, is situated between
Hole carbon, microporous carbon, graphene it is one or more, sulfur family simple substance be sulphur, selenium, tellurium it is one or more；It is calculated in mass percent,
Sulfur family simple substance accounts for 5 ~ 20% in mixed active material.
5. lithium-sulfur family mixed energy storage system according to claim 3, it is characterised in that: the preparation method of mixed active material
Are as follows: sulfur family simple substance and capacitive character porous carbon ground and mixed is uniform, it is subsequently placed in the condition of sulfur family simple substance fusion point temperature or more
Lower constant temperature, which handles 6 ~ 12h, keeps sulfur family simple substance evenly dispersed into the duct of capacitive character porous carbon.
6. lithium according to claim 1 or claim 2-sulfur family mixed energy storage system, it is characterised in that: conductive agent I be conductive carbon black,
Super-P, acetylene black, Ketjen black, electrically conductive graphite, graphene, carbon nanotube it is one or more, binder I be polytetrafluoroethyl-ne
It is alkene, Kynoar, sodium carboxymethylcellulose, polyvinyl alcohol, butadiene-styrene rubber, polyoxyethylated one or more.
7. lithium-sulfur family mixed energy storage system according to claim 2, it is characterised in that: collector I be aluminium foil, stainless (steel) wire,
One kind of carbon paper.
8. lithium-sulfur family mixed energy storage system according to claim 1, it is characterised in that: prelithiation cathode is graphite cathode pressure
The prelithiation cathode formed on lithium an- ode surface is made, the graphite cathode of prelithiation cathode in lithium-sulfur family mixed energy storage system
Face face mixes sulfur family anode；Graphite cathode is to be uniformly mixed graphite, conductive agent II, binder II to obtain mixture C and incite somebody to action
The composite graphite negative electrode or graphite cathode that mixture C compression moulding is formed are to be uniformly mixed graphite, conductive agent II, binder II
It obtains mixture D and mixture D is coated to the composite graphite negative electrode formed on collector II.
9. lithium-sulfur family mixed energy storage system according to claim 8, it is characterised in that: be calculated in mass percent, mixture C
Or graphite accounts for 80 ~ 95% in mixture D, conductive agent accounts for 2 ~ 10%, remaining is binder；Conductive agent II be conductive carbon black,
Super-P, acetylene black, Ketjen black, electrically conductive graphite, graphene, carbon nanotube it is one or more, binder II be polytetrafluoroethyl-ne
Alkene, Kynoar, sodium carboxymethylcellulose, polyvinyl alcohol, butadiene-styrene rubber, polyoxyethylated one or more, collector II
For one kind of aluminium foil, stainless (steel) wire, carbon paper.
10. lithium-sulfur family mixed energy storage system according to claim 1, it is characterised in that: lithium-sulfur family battery electrolytic solution packet
Electrolytic salt, organic solvent and lithium-sulfur family battery additive are included, electrolytic salt is lithium hexafluoro phosphate, LiBF4, hexafluoro
Arsenic acid lithium, lithium perchlorate, trifluoromethanesulfonic acid lithium, bis- (trifluoromethyl) sulfimide lithiums it is one or more；Organic solvent is chain
Shape alkyl esters, chain phosphotriester, nitrile solvents, fluorine solvent or molecular formula are R (CH2CH2O)nThe polyether class of-R',
In, n=1-6, R are methyl or ethyl, and R' is methyl or ethyl；The dielectric constant of organic solvent is not less than 30；Lithium battery diaphragm is
PP film, PE film or PP/PE/PP trilamellar membrane.
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| CN114975994A (en) * | 2022-06-17 | 2022-08-30 | 北京航空航天大学 | Low-temperature quick-charging lithium ion battery cathode material and preparation method and application thereof |
| CN116727114A (en) * | 2023-07-19 | 2023-09-12 | 昆明理工大学 | Method for recycling lepidolite through short-process flotation |
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| CN110571500B (en) * | 2019-09-18 | 2023-04-07 | 昆明理工大学 | Lithium-sulfur semi-flow battery |
| CN114975994A (en) * | 2022-06-17 | 2022-08-30 | 北京航空航天大学 | Low-temperature quick-charging lithium ion battery cathode material and preparation method and application thereof |
| CN114975994B (en) * | 2022-06-17 | 2024-02-13 | 北京航空航天大学 | Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof |
| CN116727114A (en) * | 2023-07-19 | 2023-09-12 | 昆明理工大学 | Method for recycling lepidolite through short-process flotation |
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