CN102956866B - One can fill alkali metal-sulphur flow battery - Google Patents
One can fill alkali metal-sulphur flow battery Download PDFInfo
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- CN102956866B CN102956866B CN201110249169.7A CN201110249169A CN102956866B CN 102956866 B CN102956866 B CN 102956866B CN 201110249169 A CN201110249169 A CN 201110249169A CN 102956866 B CN102956866 B CN 102956866B
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- China
- Prior art keywords
- positive electrode
- electrolyte
- positive
- flow battery
- anode
- Prior art date
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- 239000003513 alkali Substances 0.000 title claims abstract description 40
- 239000005864 Sulphur Substances 0.000 title abstract 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 220
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 239000010416 ion conductor Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 238000004891 communication Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 105
- 229910052717 sulfur Inorganic materials 0.000 claims description 85
- 239000011267 electrode slurry Substances 0.000 claims description 74
- 239000003960 organic solvent Substances 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 64
- 239000011593 sulfur Substances 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 52
- 239000006230 acetylene black Substances 0.000 claims description 51
- 239000010408 film Substances 0.000 claims description 50
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 48
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 33
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 30
- 239000002608 ionic liquid Substances 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 28
- 239000010935 stainless steel Substances 0.000 claims description 28
- 229910001220 stainless steel Inorganic materials 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 22
- 239000004020 conductor Substances 0.000 claims description 22
- 238000003411 electrode reaction Methods 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 22
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 21
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 20
- 229920000557 Nafion® Polymers 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 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 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 13
- 229920000620 organic polymer Polymers 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 10
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 5
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 claims description 5
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002931 mesocarbon microbead Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910016323 MxSy Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- FRZPYEHDSAQGAS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 FRZPYEHDSAQGAS-UHFFFAOYSA-M 0.000 claims description 3
- CEUSKOBNWAYSOJ-UHFFFAOYSA-N 1-propylpiperidine trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.C(CC)N1CCCCC1 CEUSKOBNWAYSOJ-UHFFFAOYSA-N 0.000 claims description 3
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910016861 F9SO3 Inorganic materials 0.000 claims description 3
- 229910003253 LiB10Cl10 Inorganic materials 0.000 claims description 3
- 229910001559 LiC4F9SO3 Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910010937 LiGaCl4 Inorganic materials 0.000 claims description 3
- 229910021447 LiN(CxF2x+1SO2)(CyF2y+1SO2) Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- AEHVMUMGWLAZNV-UHFFFAOYSA-N ethyl propan-2-yl carbonate Chemical compound CCOC(=O)OC(C)C AEHVMUMGWLAZNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 3
- 239000006262 metallic foam Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- VOTMQEYXFDXKIP-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCN1C=C[N+](C)=C1 VOTMQEYXFDXKIP-UHFFFAOYSA-M 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- CAVPTISELCJZGX-UHFFFAOYSA-N 1-ethyl-3-methylimidazol-3-ium;methanetricarbonitrile Chemical compound N#CC(C#N)C#N.CCN1C=C[N+](C)=C1 CAVPTISELCJZGX-UHFFFAOYSA-N 0.000 claims 1
- 239000002001 electrolyte material Substances 0.000 claims 1
- 229910009160 xLi2S Inorganic materials 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000012530 fluid Substances 0.000 abstract 2
- 238000004513 sizing Methods 0.000 abstract 2
- 239000006256 anode slurry Substances 0.000 description 61
- 239000013543 active substance Substances 0.000 description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 32
- 229910001416 lithium ion Inorganic materials 0.000 description 32
- 229910003002 lithium salt Inorganic materials 0.000 description 29
- 159000000002 lithium salts Chemical group 0.000 description 28
- 239000006183 anode active material Substances 0.000 description 19
- 229910003480 inorganic solid Inorganic materials 0.000 description 18
- 229910021131 SiyP3−yO12 Inorganic materials 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 101150047356 dec-1 gene Proteins 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 13
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 13
- 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 13
- 239000011149 active material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920001021 polysulfide Polymers 0.000 description 11
- 239000002227 LISICON Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000005077 polysulfide Substances 0.000 description 10
- 150000008117 polysulfides Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- 229910008026 Li1+x+yAlxTi2-xSiyP3-yO12 Inorganic materials 0.000 description 1
- 229910008043 Li1+x+yAlxTi2−xSiyP3-yO12 Inorganic materials 0.000 description 1
- 229910006188 Li1+x+yAlxTi2−xSiyP3−yO12 Inorganic materials 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
One can fill alkali metal-sulphur flow battery, described battery cathode chamber part, barrier film and anode chamber part, described cathode chamber part comprises positive pole reative cell and the fluid reservoir with cathode chamber pipeline communication, described positive pole reative cell comprises, positive collector electrode and the anode sizing agent circulated between positive pole reative cell and fluid reservoir used as positive pole; Described anode chamber part is negative reaction room, comprises negative pole, negative collector electrode and electrolyte liquid; Described barrier film is single ion conductor film, is arranged between described positive pole reative cell and negative reaction room, and ensures to only have single work ionic conduction between both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made up of anode electrolyte and the positive electrode active material be blended in anode electrolyte, and described positive active material is M
xs
y(M=Li or Na; 0<x≤2; 0<y≤12) in one or more.
Description
Technical Field
The present invention relates to a chemical battery. In particular to an alkali metal-sulfur flow battery.
Background
Since the lithium ion battery is successfully developed, the lithium ion battery has the advantages of good safety, high voltage and specific energy, long charging and discharging service life and the like, so that the lithium ion battery is widely applied to portable electric appliances such as mobile phones, notebook computers, cameras and the like. With the miniaturization and portability of electronic equipment and the emergence and vigorous development of green and environment-friendly electric automobiles, higher requirements are put forward on lithium ion batteries as energy and power sources. How to further improve the specific capacity and the discharge performance with high rate of the lithium ion battery on the existing basis becomes a current hot problem. In addition, how to improve the adaptability of the electronic and power equipment adopting the lithium ion battery power system to the temperature so that the electronic and power equipment can normally operate or work in a harsher outdoor environment is also a problem which needs to be solved urgently at present. The positive electrode material as an important component of the lithium ion battery is a key restriction factor for determining the performance of the lithium ion battery.
The lithium ion battery anode material which is commercially used at present mainly focuses on transition metal lithium-embedded oxides, including oxides of cobalt, iron, nickel, manganese and doping compounds thereof, but the compounds are limited by self theoretical capacity and are improved to 300Wh/Kg of energy density at most, and because the materials are solid, ions are controlled by diffusion in the charging and discharging process, the rate performance is difficult to improve and the space is not large, and in addition, because the diffusion process of lithium ions is greatly influenced by temperature change in the diffusion process, the temperature use range of the lithium ion battery is very limited. Lithium sulfur battery due to its high energy density (S)81675mAh/g), the theoretical energy density can reach 2800Wh/kg, which is considered as the development direction of future lithium ion batteries, but the system is still in the laboratory stage at present due to the larger technical difficulty. The main problems of the method are as follows: 1) charged product elemental sulfur S8And discharge product Li2The S conductivity is similar to an insulator, the conductivity is very poor, and the S-type conductive material can work if a large amount of conductive materials are compounded as an active substance, or the S-type conductive material is reduced to a nanometer level or a molecular level. In addition, polysulfide ions of the discharge product are easily dissolved in electrolyte, and non-conductive elemental sulfur or polysulfide compounds are deposited on the surface of the conductive agent during charging, so that the resistance among conductive agent particles and between the conductive agent and a current collector is increased. And along with the increase of the charging and discharging times, the internal resistance of the battery is continuously increased, and the specific energy is gradually reduced, which is the main reason for short cycle life of the lithium-sulfur batteryThus, the method is simple and easy to operate. 2) The reaction of the charging and discharging process of the elemental sulfur of the cathode material is a multi-step reaction, and the intermediate product Li2S8、Li2S6、Li2S4The electrolyte is easy to dissolve in the electrolyte, and polysulfide ions dissolved in the electrolyte can shuttle back and forth between the positive electrode and the negative electrode, so that the charge-discharge efficiency is not high, and the self-discharge is larger. How to retain polysulfide ions in the positive electrode as much as possible and enable the deposited elemental sulfur to not influence the electron transport of the positive electrode during charging and discharging are the key points for improving the cycle life of the lithium-sulfur battery.
The traditional lithium-sulfur battery technology is adopted, and the method specifically comprises the following steps:
mixing the elemental sulfur powder and the porous carbon according to the weight ratio of 1: 1, preserving heat for 24 hours at 155 ℃ under the argon condition, taking the obtained material as a positive active substance, mixing the material with acetylene black and polyvinylidene fluoride according to the weight ratio of 8: 1, coating the mixture on a current collector aluminum foil, and baking the current collector aluminum foil in vacuum at 60 ℃ for 10 hours to obtain a positive electrode.
The assembly was carried out using a standard button cell CR3032, the electrolyte was dissolved as TEGDME using 1mol/L LiTFSI and the negative electrode was a lithium sheet.
When the composite material is charged and discharged at a C/10 multiplying power constant current, 612mAh/g of the composite material is discharged in the first week, but the overcharge is obvious due to a strong shuttle effect, the first week efficiency is 137%, and the specific capacity retention rate is only 51% after 50 weeks.
Disclosure of Invention
In view of the above problems of the conventional lithium sulfur battery, the present invention is directed to an alkali metal-sulfur flow battery using elemental sulfur or an alkali metal sulfur compound as a positive electrode active material and circulating the active material in a liquid or slurry form.
A rechargeable alkali-sulfur flow battery, the battery comprising a positive electrode chamber portion, a membrane, and a negative electrode chamber portion, the positive electrode chamber portion comprising a positive electrode reaction chamber and a liquid storage tank in communication with the positive electrode chamber, the positive electrode reaction chamber comprising a positive electrode collector and a positive electrode slurry used as a positive electrode that circulates between the positive electrode reaction chamber and the liquid storage tank; the negative electrode chamber part is a negative electrode reaction chamber and comprises a negative electrode, a negative electrode collector and a negative electrode electrolyte; the diaphragm is a single-ion conductor film and is arranged between the anode reaction chamber and the cathode reaction chamber, and only single working ions are conducted between the anode and the cathode, and no other substance of non-working ions is transmitted; the positive electrode slurry is composed of positive electrode electrolyte and positive electrode active substances mixed in the positive electrode electrolyte, wherein the positive electrode active substances are one or more of MxSy (M is Li or Na; 0 is more than x and less than or equal to 2; and 0 is more than y and less than or equal to 12).
Further, the positive electrode slurry also comprises a positive electrode conductive substance; the positive electrode conductive substance is a carbon material: acetylene black, graphite, graphene, porous carbon, carbon nanotubes, carbon fibers, nitrogen-doped carbon, or a mixture thereof.
Further, the additive amount of the positive electrode conductive substance is 0-50% of the volume of the positive electrode electrolyte, and the preferable range is as follows: 0 to 30 percent.
Further, the positive electrode reaction chamber further comprises a positive electrode conductive substance arranged on the positive electrode collector, wherein the conductive substance is a carbon material: acetylene black, graphite, graphene, porous carbon, carbon nanotubes, carbon fibers, nitrogen-doped carbon, or a mixture thereof.
Further, the concentration range of the positive electrode active material in the electrolyte is as follows: 0.01-10mol/L, preferably range: 0.1 to 3 mol/L.
Further, the negative electrode is metallic lithium or metallic sodium or an alloy thereof.
Further, the single ion conductor membrane allows only the transport of a single working ion, without diffusion of other liquids and non-working ions; the single ion conductor membrane is an inorganic ceramic membrane, an organic polymer membrane or an inorganic/organic composite ceramic membrane.
Further, the inorganic ceramic membrane is a single ion conductor inorganic ceramic membrane (xLi)2S+ySiS2+zLi3PO4(0＜x≤1，0＜y≤1，0＜z≤1)、lLi2S+mGeS2+nP2S5(0＜l≤1，0＜m≤1，0＜n≤1)、hLi2S+kSiS2+jP2S5(0＜h≤1，0＜k≤1，0＜j≤1)、aLi2O+bSiO2+cTiO2+dAl2O3+eP2O5(a is more than 0 and less than or equal to 1, b is more than 0 and less than or equal to 1, c is more than 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and e is more than 0 and less than or equal to 1); the organic polymer film is a single ion conduction organic film (such as a perfluorinated ion exchange membrane (Nafion) film subjected to lithiation or sodium treatment, and the organic/inorganic composite film is a single ion conduction organic/inorganic composite film (such as a layer of inorganic Al with adjustable thickness is deposited on the organic (Nafion) film by an atomic layer deposition technology)2O3。
Further, the electrolyte in the positive and negative electrode electrolytes is one or more selected from the group consisting of: LiPF6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiAlCl4、LiGaCl4、LiB10Cl10、LiCF3SO3、LiC4F9SO3、LiN(CxF2x+1SO2)(CyF2y+1SO2) Wherein x and y are natural numbers, LiBFz (CF)3)4-zWherein z is a natural number not greater than 4; the sodium salt is: NaPF6、NaBF4、NaClO4、NaAlCl4、NaCF3SO3、NaC4F9SO3The concentration of the electrolyte is 0.5-5.0 mol/L.
Further, the solvent in the electrolyte is an organic solvent or an ionic liquid.
Further, the organic solvent used in the organic electrolytic solution is selected from one or more of the following: propylene Carbonate (PC), Ethylene Carbonate (EC), Butylene Carbonate (BC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), di-n-propyl carbonate (DPC), diisopropyl carbonate (DIPC), Ethyl Propyl Carbonate (EPC), ethyl isopropyl carbonate (EIPC), Dimethoxyethane (DME), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), diethylene glycol dimethyl ether (DGM), triethylene glycol dimethyl ether (TGM), tetraethylene glycol dimethyl ether (TEGM), dimethyl sulfoxide (DMSO), sulfolane (TMSO), dimethyl sulfone (MSM), 1, 3-dioxolane (1, 3-DOL).
Further, the ionic liquid is composed of one or more of the following types: imidazole-type ionic liquids, e.g. 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIM]BF41-butyl-3-methylimidazolium tetrafluoroborate [ BMIM ]]BF41-Ethyl-3-methylimidazolium tricyanometalate ([ EMIM ]]TCCN, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ EMIM]Tf2N, trihexyltetradecylphosphonium tetrazolium salt [ P66614][Tetz]Trihexyltetradecylphosphonium imidazolium salt [ P66614 ]][Im]1-ethyl-3-methylimidazolium tetrazolium salt [ EMIM][Tetz]1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ BMIM ]]Tf2N, 1-butyl-3-methylimidazolium hexafluorophosphate [ BMIM ]]PF61-butyl-3-methylimidazolium trifluoromethanesulfonate [ BMIM ]]OTF, 1-butyl-3-methylimidazolium dicyandiamide salt [ BMIM]DCN, 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ C8MIM]Tf2N, 1-hexyl-3-methylimidazolium tosylate [ C ]salt6MIM]OTS, 1-butyl-3-methylimidazolium N, N-dialkyldithiocarbamates [ C4MIM]BDTC, 1-butyl-3-methylimidazolidinyl trithiocarbonate [ C4MIM]TTC, 1-butyl-3-methylimidazolidyloxydithiocarbonate [ C4MIM]OTDC; pyridine type ionic liquids such as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; piperidine type ionic liquids, e.g. N-methyl, propylpiperidine bistrifluoromethanesulfonylimide PP13TFSI, N-methyl, propylpiperidine triflate PP13OTF, N-methyl, propyl piperidine hexafluorophosphate PP13PF6N-methyl, propyl piperidine brominated PP13Br; pyrrolidine ionic liquids, e.g. N-methyl, butylpyrrolidine bistrifluoromethanesulfonylimide salt BMPTf2N, brominated N-methyl, butylpyrrolidine, chlorinated N-methyl, butylpyrrolidine; quaternary ammonium type ionic liquids such as tetrabutylammonium tetrafluoroborate.
Furthermore, the positive and negative current collectors are made of a mesh or foil composed of metals such as nickel, stainless steel, titanium, aluminum and the like and alloys thereof, or metal foams or porous metals based on the metals and the alloys thereof, or carbon-based negative electrode materials.
Further, the carbon-based negative electrode material is composed of one or a mixture of a plurality of graphite, mesocarbon microbeads (MCMB), hard carbon spheres, porous carbon, acetylene black, graphene, carbon nanotubes, carbon fibers, nitrogen-doped carbon and the like.
Further, the negative pole chamber part also comprises a negative pole liquid storage tank communicated with the negative pole chamber through a pipeline.
Further, the material used for the liquid storage tank adopted by the anode part can be metal or alloy thereof such as aluminum, aluminum alloy, titanium alloy and stainless steel, or other organic polymer materials such as polytetrafluoroethylene and PVP, or inorganic ceramic composite materials.
The invention utilizes alkali metal sulfide MxSy(M ═ Li or Na; 0 < x.ltoreq.2; 0 < y.ltoreq.12) in different stages of the solubility in the electrolyte, i.e. the polysulphide is dissolved in an organic electrolyte, e.g. S8-M2S12-M2S8-M2S6-M2S4-M2S2-M2S in addition to elemental sulfur, solubility decreases in sequence with increasing alkali metal content of the polysulfide. If the concentration of polysulfide in the electrolyte reaches a certain level, when the content of alkali metal in the polysulfide gradually increases at the end of discharge, the alkali metal polysulfide is separated out from the electrolyte, and the whole reaction process shows a liquid-solid cross-mixing reaction. On the one hand, if the depth of discharge is controlled appropriately, e.g. by limiting the capacitance only M is achieved2S8-M2S4The reactants are always in a liquid state by conversion, so that the fluidity can be improved to a certain extent, and the dynamic performance is improved. On the other hand, if the reaction process is not controlled, the solid active substance may be slurriedThe material flows to achieve the purpose of circulation. Therefore, the system is a chemical system capable of controlling the reaction process, and reversible circulation between any two polysulfide compounds of alkali metal or between elemental sulfur and sulfide can be realized by controlling the discharge depth, limiting the capacity and the like.
Compared with the prior art, the invention has the following remarkable advantages:
(1) high energy density
As can be seen from table 1, sulfur and its related lithium-sulfur compounds have a theoretical specific capacity several times higher than that of the conventional positive electrode material, and even if the operating voltage is relatively low, such as about 2V, the output energy density is far higher than that of the conventional solid positive electrode material after being converted. In addition, because of the adoption of a liquid flow system, the specific gravity of a current collector in the system is greatly reduced, and therefore, compared with a conventional lithium ion battery system, the energy density of the battery system is improved, and the space is enlarged.
Table 1 comparison of prior art cathode materials with alkali metal sulfur-based materials
(2) Long cycle life
Because the positive electrode chamber and the negative electrode chamber are separated by the single ion conductor film, only single working ions are transmitted between the two chambers, and no other liquid or non-working ions are diffused, the reaction of active substances and alkali metals is effectively solved, the shuttle effect of polysulfide ions between the positive electrode and the negative electrode is avoided, the coulomb efficiency of charging and discharging is ensured to be close to one hundred percent, and the problem of poor cycle performance of the lithium-sulfur battery is fundamentally and completely solved.
(3) Wide range of service temperature
Because the traditional solid active substance is controlled by lithium ion diffusion, especially the ionic conductance is rapidly reduced along with the reduction of temperature, so that the traditional solid electrode material is greatly influenced by the temperature and has poor low-temperature electrochemical performance. The battery adopts active materials and a battery system, and the conductivity is not obviously influenced by temperature change, so that the battery has better high-temperature and low-temperature performances.
Drawings
FIG. 1 is a schematic diagram of a first embodiment of an alkali metal-sulfur flow battery of the present invention;
FIG. 2 is a schematic view of a second embodiment of the alkali metal-sulfur flow battery of the present invention;
FIG. 3 is a schematic diagram of a third embodiment of an alkali metal-sulfur flow battery of the present invention;
FIG. 4 is a schematic view of a fourth embodiment of the alkali metal-sulfur flow battery of the present invention;
FIG. 5 shows Li as an active material in the battery of FIG. 22S8When the conductive substance is acetylene black, measuring a typical first-cycle charge-discharge curve chart;
FIG. 6 shows Li as an active material in the battery of FIG. 4 according to the present invention2S8Typical first cycle charge and discharge curves measured.
Detailed Description
Example 1
As shown in figure 1 of the drawings, in which,the alkali-chargeable metal-sulfur flow battery in the present embodiment includes: positive electrode chamber part 1, diaphragm 2, negative electrode chamber part 3. The positive electrode part chamber 1 mainly comprises a liquid storage tank 11, a positive electrode reaction chamber 12, and a piston pump 13 and a flow valve 14 which are arranged on a pipeline for communicating the liquid storage tank 11 with the reaction chamber 12. The positive electrode is positive electrode slurry circulating between the positive electrode reaction chamber 12 and the liquid storage tank 11, the positive electrode slurry consists of positive electrode electrolyte and positive electrode active substance mixed in the positive electrode electrolyte, wherein the positive electrode active substance is MxSy(M is Li or Na; x is more than 0 and less than or equal to 2; y is more than 0 and less than or equal to 12). when the device is used, the device needs to be pumped into the positive electrode reaction chamber 12 through a piston pump, and the flow rate can be controlled through a flow valve 14. The positive collector electrode 16 is also provided with a conductive substance 15; the conductive material 15 is a porous, conductive material coated or rolled on the current collector 16 by an adhesive; the anode chamber has the functions of increasing the reaction area in the anode chamber, improving the conductivity of the collector electrode and improving the reaction efficiency of active substances in the anode electrolyte. The separator 2 is provided between the positive and negative electrodes as a positive and negative electrode connecting portion; the diaphragm 2 is a single ion conductor film, and the diaphragm 2 is required to ensure that only single ions are conducted between the anode and the cathode without any other substance transmission. The negative electrode chamber 3 is a closed reaction chamber; including an anode 31, a current collector 32, and an anode electrolyte 33 disposed within the anode compartment.
Positive electrode reaction chamber 1:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4(ii) a The concentration is 1 mol/L.
Adding a positive electrode active substance into the positive electrode electrolyte to obtain Li with a molar ratio of 1: 72S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S8。
In the positive electrode reaction chamber, a positive electrode conductive substance acetylene black is also arranged on a current collector, and the specific arrangement mode is that 100mg of acetylene black and a binder PTFE polytetrafluoroethylene are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode current collector.
The positive electrode collector was a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
the separator 2 in this example is an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber part 3
The negative electrode chamber is a closed reaction chamber, the negative electrode electrolyte is organic solvent PC and DMC which are 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. The negative electrode adopts a metal lithium sheet.
Example 2:
the battery structure and the like in this example are substantially the same as those in example 1, and the difference is that the composition of the positive electrode slurry used in this example is different from that in example 1, specifically:
positive electrode reaction chamber 1:
the positive electrode is positive electrode slurry circulating between the positive electrode chamber and the liquid storage tank, wherein the positive electrode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4. The concentration is 1 mol/L.
Adding a positive electrode active substance into the positive electrode electrolyte to obtain Li with a molar ratio of 1: 112S and S, mixing to form anode slurry, and adding Li with the active substance concentration of 1mol/L into the anode slurry2S12。
In the positive reaction chamber, a positive conductive material acetylene black is also arranged on a current collector, and the specific arrangement mode is that 100mg of acetylene black and adhesive PTFE polytetrafluoroethylene are mixed according to the weight ratio of 9: 1 and then rolled on a stainless steel mesh of 100 meshes to manufacture the positive conductive material acetylene black.
And (3) a diaphragm 2:
the separator 2 in this example is an inorganic solid ceramic lithium ion conductor film (LI)SICON)LiCGC(Li1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber part 3
The negative electrode chamber is a closed reaction chamber, the negative electrode electrolyte is organic solvent PC and DMC which are 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. The negative electrode adopts a metal lithium sheet.
Example 3:
the battery structure and the like in this example are substantially the same as those in example 1, and the difference is that the composition of the positive electrode slurry used in this example is different from that in example 1, specifically:
positive electrode reaction chamber 1:
the positive electrode is positive electrode slurry circulating between the positive electrode chamber and the liquid storage tank, wherein the positive electrode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4. The concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 9 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S10。
In the positive reaction chamber, a positive conductive substance acetylene black is also arranged on a positive current collector, and the specific arrangement mode is that 100mg of acetylene black and a binder PTFE polytetrafluoroethylene are mixed according to the weight ratio of 9: 1 and then are rolled on the positive current collector.
The positive electrode current collector is a 100-mesh stainless steel net.
And (3) a diaphragm 2:
the separator 2 in this example is an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber part 3
The negative electrode chamber is a closed reaction chamber, the negative electrode electrolyte is organic solvent PC and DMC which are 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. The negative electrode adopts a metal lithium sheet.
Example 4:
the battery structure and the like in this example are substantially the same as those in example 1, and the difference is that the composition of the positive electrode slurry used in this example is different from that in example 1, specifically:
positive electrode reaction chamber 1:
the positive electrode is positive electrode slurry circulating between the positive electrode chamber and the liquid storage tank, wherein the positive electrode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4. The concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 5 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.3mol/L is added into the anode slurry2S6。
In the positive reaction chamber, a positive conductive substance acetylene black is also arranged on a positive current collector, and the specific arrangement mode is that 100mg of acetylene black and a binder PTFE polytetrafluoroethylene are mixed according to the weight ratio of 9: 1 and then are rolled on the positive current collector.
The positive electrode current collector is a 100-mesh stainless steel net.
And (3) a diaphragm 2:
the separator 2 in this example is an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber part 3
The negative electrode chamber is a closed reaction chamber, the negative electrode electrolyte is organic solvent PC and DMC which are 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. The negative electrode adopts a metal lithium sheet.
Example 5:
the battery structure and the like in this example are substantially the same as those in example 1, and the difference is that the composition of the positive electrode slurry used in this example is different from that in example 1, specifically:
positive electrode reaction chamber 1:
the positive electrode is positive electrode slurry circulating between the positive electrode chamber and the liquid storage tank, wherein the positive electrode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4. The concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 3 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.2mol/L is added into the anode slurry2S4。
In the positive reaction chamber, a positive conductive substance acetylene black is also arranged on a positive current collector, and the specific arrangement mode is that 100mg of acetylene black and a binder PTFE polytetrafluoroethylene are mixed according to the weight ratio of 9: 1 and then are rolled on the positive current collector.
The positive electrode current collector is a 100-mesh stainless steel net.
And (3) a diaphragm 2:
the separator 2 in this example is an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber part 3
The negative electrode chamber is a closed reaction chamber, the negative electrode electrolyte is organic solvent PC and DMC which are 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. The negative electrode adopts a metal lithium sheet.
Example 6:
the battery structure and the like in this example are basically the same as those in example 1, and the difference is that the composition of the positive electrode slurry used in this example is different from that in example 1, specifically:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4. The concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 1 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.1mol/L is added into the anode slurry2S2。
Example 7(26)
The battery structure in this embodiment is basically the same as that in embodiment 1, and the composition of the positive electrode paste and the material of the other battery structures in this embodiment are different from those in embodiment 1, specifically:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is ionic liquid 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide [ EMIM ]]Tf2N, the electrolyte is lithium salt LiTFSI; the concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S8。
The positive current collector is also provided with a positive conductive substance: the porous carbon is specifically prepared by mixing 100mg of porous carbon and binder PTFE in a weight ratio of 9: 1 and rolling the mixture on nickel foam.
And (3) a diaphragm 2:
separator 2 was a lithiated nafion117 film. The specific lithiation process is as follows:
a. soaking nafion117 membrane in 3% H solution at 80 deg.C2O2Treating for 1 hour in the hydrogen peroxide solution;
b. washing with deionized water for 3 times;
c. soaking nafion117 membrane in 3% H at 80 deg.C2O2Treating in hydrogen peroxide solution for 1 hour;
d. soaking nafion117 membrane in 10% HNO at 80 deg.C3Treating in water solution for 1 hr;
e. washing with deionized water for 3 times
f. Soaking the nafion117 membrane in LiOH lithium hydroxide aqueous solution with the temperature of 80 ℃ and the concentration of 3M (/ L) for 24 hours;
g. and (4) washing with deionized water for 3 times, and drying at 50 ℃ in vacuum until the moisture on the nafion117 film is completely removed, so that the film can be used.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent TEGDME, and the electrolyte is LiPF6The concentration is 1 mol/L.
The negative electrode is a metal lithium sheet.
Example 8: (29)
a liquid flow rechargeable lithium-sulfur battery adopts the following specific processes of scheme 1:
the battery structure in this embodiment is basically the same as that in embodiment 1, and the composition of the positive electrode paste and the material of the other battery structures in this embodiment are different from those in embodiment 1, specifically:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiBF4The concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S to S, mixing to form anode slurryLi with active material concentration of 0.5mol/L is added into the electrode slurry2S8。
The positive current collector is also provided with a positive conductive substance: nitrogen-doped carbon, in particular: 100mg of nitrogen-doped carbon was mixed with a binder PTFE in a weight ratio of 9: 1 and rolled onto a 100 mesh stainless steel mesh.
And (3) a diaphragm 2: is an inorganic solid ceramic lithium ion conductor film: (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent PC and DMC is 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L.
The negative electrode is a metal lithium sheet.
Example 9:
as shown in fig. 2, the flow can be charged into an alkali metal-sulfur battery in this example, the basic structure of which is the same as in example 1. The difference between the two is that in the present embodiment, the positive electrode conductive material 15 is mixed into the positive electrode slurry and used, and circulates between the reservoir and the positive electrode reaction chamber with the positive electrode slurry.
Positive electrode chamber portion 1:
the positive electrode slurry is a positive electrode active material and a positive electrode conductive material mixed into the positive electrode electrolyte.
Anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance of 1: 7 into the anode electrolyte2S and S are mixed to form anode slurry, and Na with the active substance concentration of 1mol/L is added into the anode slurry2S8。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
The sodium treatment process of the Nafion membrane body comprises the following steps:
a. soaking the Nafion membrane in 3% H at 80 deg.C2O2Treating for 1 hour in the aqueous solution of hydrogen peroxide;
b. washing the Nafion membrane with deionized water for 3 times;
c. soaking the Nafion membrane in 3% H at 80 deg.C2O21 hour in the aqueous solution of hydrogen peroxide;
d. soaking the Nafion film in H at a concentration of 0.5M (0.5M/L2SO4Treating in water solution for 1 hr;
e. washing the Nafion membrane with deionized water for 3 times;
f. soaking the membrane in a NaOH sodium hydroxide aqueous solution with the concentration of 5M/L and the temperature of 80 ℃, and treating for 4 hours;
g. and (3) washing with deionized water for 3 times, and drying the Nafion membrane in vacuum at 50 ℃ to remove water on the Nafion membrane for use.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 10
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
the positive electrode slurry is a positive electrode active material and a positive electrode conductive material mixed into the positive electrode electrolyte.
Anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance to the anode electrolyte being 1: 112S and S are mixed to form anode slurry, and Na with the active substance concentration of 1mol/L is added into the anode slurry2S12。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 11
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
the positive electrode slurry is a positive electrode active material and a positive electrode conductive material mixed into the positive electrode electrolyte.
Anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance of 1: 9 into the anode electrolyte2S and S are mixed to form anode slurry, and Na with the active substance concentration of 0.5mol/L is added into the anode slurry2S10。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 12
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance of 1: 5 into the anode electrolyte2S and S, mixing to form anode slurry, and adding active material into the anode slurryThe substance is Na with a concentration of 0.3mol/L2S6。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 13
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance of 1: 3 into the anode electrolyte2S and S are mixed to form anode slurry, and Na with the active substance concentration of 0.2mol/L is added into the anode slurry2S4。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 14
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is sodium salt NaPF6(ii) a The concentration is 1 mol/L. Adding Na with the molar ratio of the anode active substance of 1: 1 into the anode electrolyte2S and S are mixed to form anode slurry, and Na with the active substance concentration of 0.1mol/L is added into the anode slurry2S2。
The positive electrode conductive substance is acetylene black accounting for 15% of the positive electrode slurry in volume ratio.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
the diaphragm in this example is an organic polymer sodium ion conductor film: a sodium treated Nafion membrane.
Negative electrode chamber portion 3:
the electrolyte of the negative electrode is organic solvent DMSO, and the electrolyte is NaPF6The concentration is 1 mol/L.
The negative electrode 31 is a metal sodium sheet.
Example 15
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber part:
positive electrode slurry: the solvent of the electrolyte is: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI; the concentration is 1 mol/L. Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S8。
The positive electrode conductive substance is acetylene black, and the addition amount of the acetylene black accounts for 10% of the volume ratio of the positive electrode slurry.
The positive electrode current collector is a 100-mesh stainless steel net.
And (3) a diaphragm 2:
the separator 2 is an inorganic solid ceramic lithium ion conductor film (LISICON) -LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC and DMC is 1: 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 16
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
positive electrode slurry: anode electrolyte: the solvent is ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [ BMIM]PF6The electrolyte is lithium salt LiPF6(ii) a The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 9 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S10。
And adding a positive conductive substance into the positive slurry, wherein the graphene accounts for 15% of the positive slurry in volume ratio.
The positive electrode current collector is a 200-mesh aluminum mesh.
And (3) a diaphragm 2:
the thin film in this example is a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent THF, and the electrolyte LiPF6The concentration is 1 mol/L.
The negative electrode 31 uses a metallic lithium plate.
Example 17
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 9. The components of the adopted positive electrode slurry and the materials of other battery structures are different from those of the embodiment 9, and the concrete steps are as follows:
positive electrode chamber portion 1:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI; the concentration is 1 mol/L.
Adding a positive electrode active substance S into the positive electrode electrolyte8Mixed to form positive electrode slurryActive materials are added into the positive electrode slurry to be 1mol/L in concentration.
And then adding acetylene black as a positive electrode conductive substance into the positive electrode electrolyte. The addition amount thereof was 15% by volume to the positive electrode slurry.
The positive electrode current collector adopts aluminum foil with the thickness of 50 microns.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent PC and DMC is 1: 1, and the electrolyte is LiBF4The concentration is 1 mol/L. A metallic lithium plate is used for the negative electrode 31 (no requirement for thickness or the like.
Example 18
As shown in fig. 3, the positive and separator portions of the flow rechargeable lithium-sulfur battery of this embodiment are constructed as in embodiment 1, except that the negative chamber 35 of the battery of this embodiment is connected to a negative reservoir 34, and the negative electrolyte 33 is circulated between the negative chamber 35 and the negative reservoir 34 by a piston pump 36 powered by a conduit disposed between the negative chamber 35 and the negative reservoir 34 for communicating the two.
Positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S, mixing to form anode slurry, and adding Li with the active substance concentration of 1mol/L into the anode slurry2S8。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 19
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L. Adding a certain amount of Li with a molar ratio of 1: 11 as a positive electrode active substance into the positive electrode electrolyte2S and S, mixing to form anode slurry, and adding Li with the active substance concentration of 1mol/L into the anode slurry2S12。
A certain amount of positive electrode active material Li2S and S are dissolved into the anode electrolyte according to the molar ratio of 1: 11 to form 1mol/L Li2S12。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 20
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L. Adding a certain amount of Li with a molar ratio of 1: 9 as a positive electrode active substance into the positive electrode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.5mol/L is added into the anode slurry2S10。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 21
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L. Adding a certain amount of Li with a molar ratio of 1: 5 as a positive electrode active substance into the positive electrode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.3mol/L is added into the anode slurry2S6。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 22
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L. Adding a certain amount of Li with a molar ratio of 1: 3 as a positive electrode active substance into the positive electrode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.2mol/L is added into the anode slurry2S4。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 23
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DMSO, and the electrolyte is lithium salt LiPF6. The concentration is 1 mol/L. Adding a certain amount of Li with a molar ratio of 1: 1 of positive electrode active substances into the positive electrode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance concentration of 0.1mol/L is added into the anode slurry2S2。
The positive electrode conductive substance is acetylene black, and specifically, 100mg of acetylene black and a binder PTFE are mixed according to the weight ratio of 9: 1 and then are rolled on a positive electrode collector.
Positive electrode collector electrode: 100-mesh stainless steel net.
The diaphragm portion 2:
the separator was a lithiated nafion117 film.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
Negative electrode 31 is a metallic lithium sheet.
Example 24
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
a liquid flow rechargeable lithium-sulfur battery adopts the following specific processes of scheme 3:
positive electrode chamber part:
the solvent of the electrolyte is: the solvent is ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIM]BF4The electrolyte is lithium salt LiBF4(ii) a The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 3 is added into the anode electrolyte2S and S, mixing to form anode slurry, and adding Li with the active substance concentration of 3mol/L into the anode slurry2S4。
The positive electrode conductive substance is carbon nano-tubes mixed in the positive electrode electrolyte, and the adding amount of the positive electrode conductive substance is 20% of the volume ratio of the positive electrode slurry. And the slurry was continuously stirred during charging and discharging.
The positive electrode current collector adopts a 100-mesh titanium mesh.
And (3) a diaphragm 2:
the diaphragm in the embodiment is an inorganic solid ceramic and organic composite lithium ion conductor film, and specifically is inorganic Al deposited with 3nm2O3Organic Nafion membrane of (1).
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is an organic solvent TMSO, the electrolyte is LiTFSI, and the concentration is 1 mol/L.
The negative electrode 31 uses a metallic lithium plate.
Example 25
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber portion 1:
the solvent of the positive electrolyte is as follows: the solvent is organic solvent TMSO, and the electrolyte is lithium salt LiPF6(ii) a The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S, mixing to form anode slurry, and adding 1mol/L Li active substance into the anode slurry2S8。
The positive active material is graphene, and specifically, 100mg of graphene and a binder PTFE are mixed according to a weight ratio of 9: 1 and then are rolled on a positive collector.
The positive electrode collector was a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
is a single ion conduction organic-inorganic composite film, in particular to a film provided thereonWith a layer of Al of thickness 4nm2O3Organic Nafion membrane of (1).
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L.
The negative electrode 31 uses a metallic lithium plate.
Example 26
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber portion 1:
anode electrolyte: the solvent is organic solvent TMSO and electrolyte lithium salt LiPF6(ii) a The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 11 is added into the anode electrolyte2S and S, mixing to form anode slurry, wherein the concentration of the active substance added into the anode slurry is 1 mol/L.
The positive active material is graphene, and specifically, 100mg of graphene and a binder PTFE are mixed according to a weight ratio of 9: 1 and then are rolled on a positive collector.
The positive electrode collector was a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
is an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6In a concentration of1mol/L。
The negative electrode 31 uses a metallic lithium plate.
In this example, only Li was realized by limiting the reaction concentration during the entire charge-discharge reaction of the entire battery2S12→Li2S4The circulation between the reaction materials ensures that the reaction materials are in a liquid state.
Example 27
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 18. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 18, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent TMSO, and the electrolyte is lithium salt LiPF6(ii) a The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S, mixing to form anode slurry, and adding 1mol/L Li as active substance into the anode slurry2S8。
The positive active material is graphene, and specifically, 100mg of graphene and a binder PTFE are mixed according to a weight ratio of 9: 1 and then are rolled on a positive collector.
The positive electrode collector was a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
the thin film in this example was an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12) The positive and negative electrodes are isolated.
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, electrolyzingThe quality is LiPF6The concentration is 1 mol/L.
The negative electrode 31 uses a metallic lithium plate.
In this example, only Li was realized by limiting the reaction concentration during the entire charge-discharge reaction of the entire battery2S8→Li2S4The circulation between the reaction materials ensures that the reaction materials are in a liquid state.
Example 28
As shown in fig. 4, the flow can be charged into an alkali metal-sulfur battery in this example, the basic structure of which is the same as in example 8. The difference between the two is in the manner of disposing the conductive material 15 and the composition of the electrolyte and the active material. In this embodiment, the positive electrode conductive material 15 is mixed with the positive electrode slurry and circulated between the positive electrode chamber and the positive electrode reservoir along with the positive electrode slurry during the operation of the battery.
Positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 7 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance of 0.5mol/L is added into the anode slurry2S8。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 29
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 11 is added into the anode electrolyte2S and S, mixing to form anode slurry, and adding 1mol/L Li as active substance into the anode slurry2S12。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 30
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 9 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance of 0.5mol/L is added into the anode slurry2S10。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 31
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 5 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance of 0.3mol/L is added into the anode slurry2S6。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 32
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 3 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance of 0.2mol/L is added into the anode slurry2S4。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 33
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber part:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI. The concentration is 1 mol/L.
Li with the molar ratio of the anode active material of 1: 1 is added into the anode electrolyte2S and S are mixed to form anode slurry, and Li with the active substance of 0.2mol/L is added into the anode slurry2S4。
The conductive substance of the positive electrode is acetylene black, and the adding amount of the conductive substance accounts for 10% of the volume ratio of the positive electrode slurry.
Positive current collector 16 is a 100 mesh stainless steel mesh.
And (3) a diaphragm 2:
using an inorganic solid ceramic lithium ion conductor film LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is organic solvent EC to DEC 1 to 1, and the electrolyte is LiPF6The concentration is 1 mol/L. Negative electrode 31 is a metallic lithium sheet.
Example 34
The flow in this example can be charged as an alkali metal-sulfur cell, the basic cell structure being the same as in example 28. The components of the positive electrode slurry and the materials of other battery structures are different from those of example 28, specifically:
positive electrode chamber portion 1:
anode electrolyte: the solvent is organic solvent DOL and DME are 1: 1, and the electrolyte is lithium salt LiTFSI; the concentration is 1 mol/L.
Adding Li as positive electrode active substance into the electrolyte2And S, mixing to form positive electrode slurry, wherein the concentration of the active substance added into the positive electrode slurry is 1 mol/L.
And then adding acetylene black as a positive electrode conductive substance into the positive electrode electrolyte. The addition amount thereof was 40% by volume to the positive electrode slurry.
The positive electrode current collector adopts 100-micron aluminum foil.
And (3) a diaphragm 2:
the separator in this example was an inorganic solid ceramic lithium ion conductor film (LISICON) LiCGC (Li)1+x+yAlxTi2-xSiyP3-yO12)。
Negative electrode chamber portion 3:
and (3) cathode electrolyte: the solvent is an organic solvent with the ratio of EC to DEC being 1 to 1; the electrolyte is LiPF6(ii) a The concentration is 1 mol/L. The negative electrode 31 uses a metallic lithium plate.
TABLE 2 first week discharge aptitude and 50 week capacity retention ratio of each battery of the above examples
| Illustration of | First cycle discharge inverse capacity (mAh/g) | 50-week capacity retention (%) |
| Example 1 | 938 | 97％ |
| Example 2 | 1064 | 96％ |
| Example 3 | 1015 | 94％ |
| Example 4 | 798 | 92％ |
| Example 5 | 712 | 89％ |
| Example 6 | 498 | 84％ |
| Example 7 | 935 | 96％ |
| Example 8 | 945 | 94％ |
| Example 9 | 899 | 94％ |
| Example 10 | 969 | 92％ |
| Example 11 | 815 | 88％ |
| Example 12 | 723 | 87％ |
| Example 13 | 569 | 82％ |
| Example 14 | 452 | 80％ |
| Example 15 | 956 | 95％ |
| Example 16 | 867 | 91％ |
| Example 17 | 986 | 78％ |
| Example 18 | 945 | 86％ |
| Example 19 | 1040 | 95％ |
| Example 20 | 802 | 92％ |
| Example 21 | 732 | 90％ |
| Example 22 | 785 | 89％ |
| Example 23 | 446 | 82％ |
| Example 24 | 653 | 85％ |
| Example 25 | 952 | 94％ |
| Example 26 | 258 | 96％ |
| Example 27 | 194 | 97％ |
| Example 28 | 909 | 93％ |
| Example 29 | 1012 | 89％ |
| Example 30 | 986 | 85％ |
| Example 31 | 803 | 82％ |
| Example 32 | 756 | 79％ |
| Example 33 | 452 | 75％ |
| Example 34 | 823 | 79％ |
The standard button cell CR3032 obtained by adopting the traditional lithium-sulfur battery process is assembled, wherein electrolyte is dissolved into TEGDME by adopting 1mol/L LiTFSI, and a lithium sheet is taken as a negative electrode. When the composite material is charged and discharged at a C/10 multiplying power constant current, 612mAh/g of the composite material is discharged in the first week, but the overcharge is obvious due to a strong shuttle effect, the first week efficiency is 137%, and the specific capacity retention rate is only 51% after 50 weeks.
FIG. 5 shows a structure of a battery of the present invention shown in FIG. 1, in which Li is used2S8Typical first cycle charge and discharge curves measured when acetylene black was used as the active material and the conductive material. FIG. 6 shows the structure of the battery of the present invention shown in FIG. 2, and employing Li2S8Typical first cycle charge and discharge curves measured when acetylene black was used as the active material and the conductive material. In fig. 6, the dotted line portion represents the initial charge of the conventional lithium-sulfur batteryDischarge curve. FIG. 7 is the cell structure of the present invention shown in FIG. 4, using Li2S8In a typical first cycle charge-discharge curve measured as an active material, a dotted line in the graph is a first cycle charge-discharge curve without a conductive additive, and a solid line is a first cycle charge-discharge curve with 20% acetylene black added. By comparing the two, the conductive additive is added to form the slurry, so that the electronic conductivity of a reaction system can be greatly improved, the charge-discharge polarization is greatly reduced, and the first-week charge-discharge capacity is greatly improved.
The electrolyte, conductive material, positive electrode collector material, separator material, electrolyte composition and concentration in the negative electrode, and negative electrode material and negative electrode collector material used in the positive electrode part of the liquid flow rechargeable lithium-sulfur battery disclosed in the present invention may be, in addition to those disclosed in the above examples:
the solvent in the solvent solution adopted by the positive electrode electrolyte is as follows: an organic solvent or an ionic liquid; wherein the organic solvent is Propylene Carbonate (PC), Ethylene Carbonate (EC), Butylene Carbonate (BC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), di-n-propyl carbonate (DPC), diisopropyl carbonate (DIPC), Ethyl Propyl Carbonate (EPC), ethyl isopropyl carbonate (EIPC), Dimethoxyethane (DME), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), diethylene glycol dimethyl ether (DGM), triethylene glycol dimethyl ether (TGM), tetraethylene glycol dimethyl ether (TEGM), dimethyl sulfoxide (DMSO), sulfolane (TMSO), dimethyl sulfone (MSM), 1, 3-dioxolane (1, 3-DOL). The ionic liquid is composed of one or more of the following types: imidazole-type ionic liquids, e.g. 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIM]BF41-butyl-3-methylimidazolium tetrafluoroborate [ BMIM ]]BF41-Ethyl-3-methylimidazolium tricyanometalate ([ EMIM ]]TCCN, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ EMIM]Tf2N, trihexyltetradecylphosphonium tetrazolium salt [ P66614][Tetz]Trihexyltetradecylphosphonium imidazolium salt [ P66614 ]][Im]1-ethyl-3-methylimidazolium tetrazolium salt [ EMIM][Tetz]1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ BMIM ]]Tf2N, 1-butyl-3-methylimidazolium hexafluoroPhosphate [ BMIM]PF61-butyl-3-methylimidazolium trifluoromethanesulfonate [ BMIM ]]OTF, 1-butyl-3-methylimidazolium dicyandiamide salt [ BMIM]DCN, 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ C8MIM]Tf2N, 1-hexyl-3-methylimidazolium tosylate [ C6MIM]OTS, 1-butyl-3-methylimidazolium N, N-dialkyldithiocarbamates [ C4MIM]BDTC, 1-butyl-3-methylimidazolidinyl trithiocarbonate [ C4MIM]TTC, 1-butyl-3-methylimidazolidyloxydithiocarbonate [ C4MIM]OTDC; pyridine type ionic liquids such as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; piperidine type ionic liquids such as N-methyl, propylpiperidine bistrifluoromethanesulfonylimide PP13TFSI, N-methyl, propylpiperidine trifluoromethanesulfonate PP13OTF, N-methyl, propylpiperidine hexafluorophosphate PP13PF6N-methyl, propylpiperidine brominated PP13 Br; pyrrolidine ionic liquids, e.g. N-methyl, butylpyrrolidine bistrifluoromethanesulfonylimide salt BMPTf2N, brominated N-methyl, butylpyrrolidine, chlorinated N-methyl, butylpyrrolidine; quaternary ammonium type ionic liquids such as tetrabutylammonium tetrafluoroborate and the like.
M can be used as the positive electrode active materialxSyWherein M ═ Li or Na; x is more than 0 and less than or equal to 2; y is more than 0 and less than or equal to 12; the positive active material can be liquid or solid or the mixture phase of the two; the concentration of the positive electrode active material in the positive electrode electrolyte is 0.01-10mol/L, and the preferable range is as follows: 0.1-3 mol/L.
The organic electrolyte of the positive electrode and the negative electrode is selected from one or more of the following electrolytes: LiPF6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiAlCl4、LiGaCl4、LiB10Cl10、LiCF3SO3LiC4F9SO3, LiN (CxF2x +1SO2) (CyF2y +1SO2) wherein x and y are natural numbers, LiBFz(CF3)4-zWherein z is a natural number not greater than 4; the sodium salt is: NaPF6、NaBF4、NaClO4、NaAlCl4、NaCF3SO3、NaC4F9SO3Lithium salt in electrolyteThe concentration of (b) is 0.5-5.0 mol/L.
The positive electrode conductive material exists in two forms in the battery, which is shown in fig. 1 and 3 as being fixed in the positive electrode reaction chamber, in which case carbon may be coated or rolled on a current collector made of metal or an alloy thereof by a binder. As shown in fig. 2 and 4, the positive conductive material can also be mixed in the positive slurry, and circulates between the positive chamber and the positive liquid storage tank along with the positive slurry in the working process of the battery, and the addition amount of the positive conductive material is 0-50% of the volume of the electrolyte system, and the preferable range is as follows: 0 to 30 percent.
The negative electrode electrolyte is a non-aqueous organic electrolyte.
The negative electrode (the active material in the negative electrode is the negative electrode) adopts metal lithium or metal sodium or the alloy thereof: lithium silicon, lithium tin alloy.
The positive and negative current collectors may be a mesh or foil made of metals such as nickel, stainless steel, titanium, aluminum, and the like, and alloys thereof, wherein the mesh is 20-500 mesh, or metal foams or porous metals based on the metals and alloys thereof, or carbon-based negative materials such as graphite, mesocarbon microbeads (MCMB), hard carbon spheres, porous carbon, acetylene black, graphene, carbon nanotubes, carbon fibers, nitrogen-doped carbon, and the like, or a mixture thereof.
The materials used by the positive electrode liquid storage tank and the negative electrode liquid storage tank can be metals or alloys thereof such as aluminum, aluminum alloy, titanium alloy and stainless steel, and can also be other organic polymer materials such as polytetrafluoroethylene and PVP, and inorganic ceramic composite materials can also be used.
The battery disclosed by the invention has the characteristics of high energy density, large specific capacity, long cycle life, low cost, high energy utilization efficiency and the like, can be widely applied to the fields of large-scale energy storage equipment required by clean energy solar energy and wind power, intelligent power grid peak shaving, distributed power stations, backup power sources, communication base stations and the like, and is particularly suitable for being used as large-scale energy storage equipment, but the scope is not limited to the large-scale energy storage equipment.
Claims (19)
1. A rechargeable alkali-sulfur flow battery, comprising a positive electrode chamber portion, a diaphragm, and a negative electrode chamber portion, wherein the positive electrode chamber portion comprises a positive electrode reaction chamber and a liquid storage tank in pipe communication with the positive electrode chamber, the positive electrode reaction chamber comprises a positive electrode collector and a positive electrode slurry used as a positive electrode and circulating between the positive electrode reaction chamber and the liquid storage tank; the negative electrode chamber part is a negative electrode reaction chamber and comprises a negative electrode, a negative electrode collector and a negative electrode electrolyte; the diaphragm is a single ion conductor film, is arranged between the positive electrode reaction chamber and the negative electrode reaction chamber and ensures positive and negative electrodesOnly single working ion is conducted between the poles, and no other non-working ion is transmitted by any substance; the positive electrode slurry is composed of positive electrode electrolyte and positive electrode active material mixed in the positive electrode electrolyte, wherein the positive electrode active material is MxSyWherein M is the element Li or Na, 0<x≤2；0<y≤12。
2. A rechargeable alkali-sulfur flow battery as claimed in claim 1, wherein said positive electrode slurry further includes a positive electrode conductive material; the positive electrode conductive substance is a carbon material: acetylene black, graphite, graphene, porous carbon, carbon nanotubes, carbon fibers, nitrogen-doped carbon, or a mixture thereof.
3. A rechargeable alkali metal-sulfur flow battery as claimed in claim 2, wherein the positive electrode conductive material is added in an amount of 0 to 50% by volume of the positive electrode electrolyte.
4. A rechargeable alkali-sulfur flow battery as claimed in claim 3, wherein the positive electrode conductive material is added in an amount of 0-30% by volume of the positive electrode electrolyte.
5. The alkali-chargeable metal-sulfur flow battery as recited in claim 1, wherein the positive reaction chamber further comprises a positive conductive substance disposed on a positive current collector, the conductive substance being a carbon material: acetylene black, graphite, graphene, porous carbon, carbon nanotubes, carbon fibers, nitrogen-doped carbon, or a mixture thereof.
6. The alkali-chargeable metal-sulfur flow battery as recited in claim 1, wherein a concentration of the positive electrode active material in the electrolyte is in a range of: 0.01 to 10 mol/L.
7. The alkali-chargeable metal-sulfur flow battery as recited in claim 6, wherein a concentration of the positive electrode active material in the electrolyte is in a range of: 0.1 to 3 mol/L.
8. The rechargeable alkali metal-sulfur flow battery as claimed in claim 1, wherein the negative electrode is metallic lithium or metallic sodium or an alloy thereof.
9. The rechargeable alkali metal-sulfur flow battery of claim 1, wherein the single ion conductor membrane allows the transport of only a single working ion without diffusion of other liquid and non-working ions; the single ion conductor membrane is an inorganic ceramic membrane, an organic polymer membrane or an inorganic/organic composite ceramic membrane.
10. The alkali-chargeable metal-sulfur flow battery as recited in claim 9, wherein the inorganic ceramic membrane is a single-ion conductor inorganic ceramic membrane; the single-ion conductor inorganic ceramic membrane is xLi2S+ySiS2+zLi3PO4、iLi2S+mGeS2+nP2S5、hLi2S+kSiS2+jP2S5Or aLi2O+bSiO2+cTiO2+dAl2O3+eP2O5Wherein 0 is<x≤1,0<y≤1,0<z≤1、0<i≤1,0<m≤1,0<n≤1、0<h≤1,0<k≤1,0<j≤1，0<a≤1,0<b≤1,0<c≤1,0≤d≤1,0<e is less than or equal to 1; the organic polymer film is a single-ion conduction organic film; the organic/inorganic composite membrane is a single ion conduction organic/inorganic composite membrane.
11. The rechargeable alkali metal-sulfur flow battery as claimed in claim 10, wherein the single ion conductive organic/inorganic composite membrane is a layer of inorganic Al with adjustable thickness disposed thereon2O3The organic Nafion membrane of (1); the single ion conductive organic film is lithiated or sodium-treatedA perfluorinated ion exchange membrane.
12. The rechargeable alkali metal-sulfur flow battery as claimed in claim 1, wherein the electrolyte in the positive and negative electrolytes is one or more selected from the group consisting of: LiPF6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiAlCl4、LiGaCl4、LiB10Cl10、LiCF3SO3、LiC4F9SO3、LiN(CxF2x+1SO2)(CyF2y+1SO2) Wherein x and y are natural numbers, LiBFz(CF3)4-zWherein z is not more than 4 and is a natural number; the sodium salt is: NaPF6、NaBF4、NaClO4、NaAlCl4、NaCF3SO3、NaC4F9SO3The concentration of the electrolyte is 0.5-5.0 mol/L.
13. The rechargeable alkali-sulfur flow battery as claimed in claim 1, wherein the solvent in the electrolyte is an organic solvent or an ionic liquid.
14. The rechargeable alkali-sulfur flow battery as claimed in claim 13, wherein the organic solvent used in the organic electrolyte is selected from one or more of the following: propylene carbonate, ethylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, sulfolane, dimethyl sulfone, 1, 3-dioxolane.
15. The chargeable alkali metal-sulfur flow battery as recited in claim 13, wherein the ionic liquid is composed of one or more of an imidazole-type ionic liquid, a pyridine-type ionic liquid, a piperidine-type ionic liquid, a pyrrolidine-type ionic liquid, and a quaternary ammonium-type ionic liquid; wherein,
the imidazole type ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIM]BF41-butyl-3-methylimidazolium tetrafluoroborate [ BMIM ]]BF41-Ethyl-3-methylimidazolium tricyanomethane salt [ EMIM]TCCN, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ EMIM]Tf2N, trihexyltetradecylphosphonium tetrazolium salt [ P66614][Tetz]Trihexyltetradecylphosphonium imidazolium salt [ P66614 ]][Im]1-ethyl-3-methylimidazolium tetrazolium salt [ EMIM][Tetz]1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ BMIM ]]Tf2N, 1-butyl-3-methylimidazolium hexafluorophosphate [ BMIM ]]PF61-butyl-3-methylimidazolium trifluoromethanesulfonate [ BMIM ]]OTF, 1-butyl-3-methylimidazolium dicyandiamide salt [ BMIM]DCN, 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt [ C8MIM]Tf2N, 1-hexyl-3-methylimidazolium tosylate [ C6MIM]OTS, 1-butyl-3-methylimidazolium N, N-dialkyldithiocarbamates [ C4MIM]BDTC, 1-butyl-3-methylimidazolidinyl trithiocarbonate [ C4MIM]TTC or 1-butyl-3-methylimidazolidyloxydithiocarbonate [ C4MIM]OTDC；
The pyridine type ionic liquid is N-ethylpyridine tetrafluoroborate or N-ethylpyridine hexafluorophosphate;
the piperidine type ionic liquid is N-methyl, propyl piperidine bis (trifluoromethyl) sulfonyl imide salt PP13TFSI, N-methyl, propyl piperidine trifluoro-methanesulfonate PP13OTF, N-methyl, propyl piperidine hexafluorophosphate PP13PF6Or N-methyl, propylpiperidine brominated PP13 Br;
the pyrrolidine ionic liquid is N-methyl, butyl pyrrolidine bistrifluoromethylsulfonyl imide salt BMPTf2N, brominated N-methyl, butylpyrrolidine, chlorinated N-methyl, butylpyrrolidine;
the quaternary ammonium type ionic liquid is tetrabutyl ammonium tetrafluoroborate.
16. The alkali-chargeable metal-sulfur flow battery as claimed in claim 1, wherein said positive and negative current collectors are made of a mesh or foil made of nickel, stainless steel, titanium, aluminum metal and their alloys, wherein the mesh is 20-500 mesh, or a metal foam or porous metal based on the above metals and their alloys, or a carbon-based negative electrode material.
17. The alkali-chargeable metal-sulfur flow battery as claimed in claim 16, wherein the carbon-based negative electrode material is composed of one or more of graphite, mesocarbon microbeads, hard carbon spheres, porous carbon, acetylene black, graphene, carbon nanotubes, carbon fibers, nitrogen-doped carbon, and the like.
18. A rechargeable alkali-sulfur flow battery as claimed in any one of the preceding claims wherein the negative chamber portion further includes a negative reservoir in communication with the negative chamber via a conduit.
19. The alkali-chargeable metal-sulfur flow battery as recited in claim 1, wherein the material of the liquid storage tank used in the positive electrode portion is aluminum, aluminum alloy, titanium alloy, stainless steel; or polytetrafluoroethylene, PVP organic polymer material or inorganic ceramic composite material.
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| US9583779B2 (en) * | 2013-02-04 | 2017-02-28 | Massachusetts Institute Of Technology | Metal sulfide electrodes and energy storage devices thereof |
| CN103227348B (en) * | 2013-04-03 | 2015-05-13 | 山东默锐科技有限公司 | Sodium-sulfur electrical storage battery |
| US9120834B2 (en) * | 2013-10-31 | 2015-09-01 | Cms Technologies Holdings, Inc. | Membrane separation of ionic liquid solutions |
| KR101558669B1 (en) * | 2013-10-31 | 2015-10-07 | 현대자동차주식회사 | A cathode for lithium sulfur battery and a method for preparing thereof |
| CN104716294B (en) * | 2013-12-15 | 2018-04-13 | 中国科学院大连化学物理研究所 | Lithium halogen fluid cell |
| CN105280942B (en) * | 2014-07-01 | 2017-11-28 | 北京好风光储能技术有限公司 | A kind of lithium double flow battery |
| CN105098140B (en) * | 2014-08-06 | 2016-08-24 | 中国科学院物理研究所 | Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes |
| CN105514531B (en) * | 2014-09-23 | 2018-07-03 | 中国科学院大连化学物理研究所 | A kind of lithium ion-halogen flow battery |
| CN106159302B (en) * | 2015-04-08 | 2019-03-29 | 北京好风光储能技术有限公司 | A kind of lithium slurry cell reaction device |
| CN106340663B (en) * | 2015-07-06 | 2019-04-09 | 中国科学院大连化学物理研究所 | A kind of list liquid stream lithium-sulfur cell |
| DE102017010031A1 (en) * | 2017-10-23 | 2019-04-25 | Iontech Systems Ag | Alkaline-ion battery, based on selected allotropes of sulfur, as well as methods of their preparation |
| CN108365247A (en) * | 2018-01-19 | 2018-08-03 | 复旦大学 | A kind of bromo- half flow battery with ion embedded type solid cathode |
| CN109546165B (en) * | 2018-12-13 | 2021-10-22 | 南开大学 | Preparation method and application of carbon felt composite electrode material for zinc-iodine flow battery |
| WO2020185482A1 (en) * | 2019-03-13 | 2020-09-17 | Eastman Chemical Company | Processes useful in the manufacture of cyclododecasulfur |
| CN110867587B (en) * | 2019-11-29 | 2022-03-01 | 常州大学 | Neutral water system mixed liquid flow battery with high power and long service life based on pyridylphenoxazine |
| CN112924434A (en) * | 2021-01-21 | 2021-06-08 | 南开大学 | Electrochemical cell for in-situ Raman test of flow battery |
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