CN111900497A - Aqueous zinc ion battery electrolyte and application thereof - Google Patents
Aqueous zinc ion battery electrolyte and application thereof Download PDFInfo
- Publication number
- CN111900497A CN111900497A CN202010538200.8A CN202010538200A CN111900497A CN 111900497 A CN111900497 A CN 111900497A CN 202010538200 A CN202010538200 A CN 202010538200A CN 111900497 A CN111900497 A CN 111900497A
- Authority
- CN
- China
- Prior art keywords
- zinc
- electrolyte
- concentration
- salt
- aqueous
- Prior art date
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- Pending
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 186
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 161
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011701 zinc Substances 0.000 claims abstract description 70
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical group [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 64
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 150000003751 zinc Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003115 supporting electrolyte Substances 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 238000012983 electrochemical energy storage Methods 0.000 claims description 14
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 13
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 239000013538 functional additive Substances 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011670 zinc gluconate Substances 0.000 claims description 5
- 235000011478 zinc gluconate Nutrition 0.000 claims description 5
- 229960000306 zinc gluconate Drugs 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229940045136 urea Drugs 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 19
- 238000004090 dissolution Methods 0.000 abstract description 13
- 238000007614 solvation Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 239000002002 slurry Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000006230 acetylene black Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- -1 fluorosulfonyl Chemical group 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DNCCTZUJYVETRT-UHFFFAOYSA-J Cl(=O)(=O)(=O)[O-].[Zn+2].[Zn+2].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical compound Cl(=O)(=O)(=O)[O-].[Zn+2].[Zn+2].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] DNCCTZUJYVETRT-UHFFFAOYSA-J 0.000 description 1
- 229910002548 FeFe Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102000040945 Transcription factor Human genes 0.000 description 1
- 108091023040 Transcription factor Proteins 0.000 description 1
- ROZPZBUZWPOKFI-UHFFFAOYSA-M [Cl-].[Fr+] Chemical compound [Cl-].[Fr+] ROZPZBUZWPOKFI-UHFFFAOYSA-M 0.000 description 1
- IBTDLPRFBAMMJB-UHFFFAOYSA-M [Fr+].CC([O-])=O Chemical compound [Fr+].CC([O-])=O IBTDLPRFBAMMJB-UHFFFAOYSA-M 0.000 description 1
- IXHYSEYEWBXTCP-UHFFFAOYSA-L [Fr+].[Fr+].[O-]S([O-])(=O)=O Chemical compound [Fr+].[Fr+].[O-]S([O-])(=O)=O IXHYSEYEWBXTCP-UHFFFAOYSA-L 0.000 description 1
- LBGACZYWAQIGPS-UHFFFAOYSA-N [Fr+].[O-][N+]([O-])=O Chemical compound [Fr+].[O-][N+]([O-])=O LBGACZYWAQIGPS-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- WSLQHGMJTGELSF-UHFFFAOYSA-L dipotassium;difluoride Chemical compound [F-].[F-].[K+].[K+] WSLQHGMJTGELSF-UHFFFAOYSA-L 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- RBUOVFCQLHVYOQ-UHFFFAOYSA-J dizinc disulfate Chemical compound [Zn+2].[Zn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RBUOVFCQLHVYOQ-UHFFFAOYSA-J 0.000 description 1
- WLBHJIHRLZNSIV-UHFFFAOYSA-J dizinc tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Zn+2].[Zn+2] WLBHJIHRLZNSIV-UHFFFAOYSA-J 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The application discloses a water-based zinc ion battery electrolyte and application thereof. The electrolyte of the water-based zinc ion battery contains solvent water, high-concentration electrolyte salt and zinc salt; the zinc salt is water-soluble salt; the high-concentration electrolyte salt is potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate, and the mass molar concentration of the electrolyte salt is not less than 10 mol/kg. According to the electrolyte, due to the addition of high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate, a large amount of water molecules in the electrolyte can be consumed due to the strong solvation effect of the electrolyte, the hydration effect of zinc ions is reduced, and zinc dendrites formed by the zinc ions in dissolution and deposition are inhibited; in addition, the strong solvation effect of the high-concentration electrolyte salt and solvent water molecules can reduce the electrochemical activity of the water molecules, improve the electrochemical window of the electrolyte, play a role in reducing hydrogen evolution reaction and zinc dissolution, inhibit the decomposition of the water molecules on the surface of an electrode, reduce the corrosion and dissolution of a zinc cathode and improve the cycle life of a water-system zinc ion battery.
Description
Technical Field
The application relates to the field of water-system zinc ion batteries, in particular to a water-system zinc ion battery electrolyte and application thereof.
Background
The zinc ion battery based on the water-based electrolyte is a novel energy storage system with low cost, high safety and high cost performance, and is expected to replace the existing energy storage technology. At present, the aqueous zinc ion battery electrolyte mainly comprises zinc sulfate, zinc trifluoromethanesulfonate, zinc perchlorate, zinc chloride, zinc acetate, zinc nitrate and the like. In which ZnSO4Is mainly characterized in that the positive electrode can generate discharge byproduct Zn4(OH)6SO4·nH2O, and the negative electrode has a relatively significant zinc dendrite problem. Zn (CF)3SO3)2Has the main disadvantages of high price and high cost; and, its solubility is low, resulting in a low electrolyte voltage window. Zn (ClO)4)2Has the major disadvantage of having a high overpotential. ZnCl2And Zn (CH)3COO)2Has the main disadvantages of poor anion stability, poor electrochemical performance of the battery and low coulombic efficiency. Zn (NO)3)2The main disadvantage of (2) is that nitrate radical has strong oxidizing property, which can cause the performance degradation of zinc cathode, and further cause the low coulombic efficiency of the cathode.
Therefore, how to effectively reduce the corrosion and dissolution of zinc, inhibit the growth of zinc dendrites, and improve the cycle life of the aqueous zinc ion battery remains a major and difficult point of research on the aqueous zinc ion battery.
Disclosure of Invention
The application aims to provide an improved water-based zinc ion battery electrolyte and application thereof.
The following technical scheme is adopted in the application:
the first aspect of the application discloses an aqueous zinc ion battery electrolyte, which contains water, high-concentration electrolyte salt and zinc salt; wherein, water is a solvent of the electrolyte, and the zinc salt is water-soluble salt; the high-concentration electrolyte salt is potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate, and the molarity of the high-concentration electrolyte salt is not less than 10 mol/kg. It is understood that in the electrolyte of the present application, the high concentration electrolyte salt may be one having a molality of not less than 10mol/kgBis (fluorosulfonyl) imide potassium salt (F)2NO4S2K, abbreviation KFSI); or potassium trifluoromethanesulfonate (CF) having a molar mass concentration of not less than 10mol/kg3KO3S); or the electrolyte simultaneously contains potassium bis (fluorosulfonyl) imide and potassium trifluoromethanesulfonate, and the total mass molar concentration of the potassium bis (fluorosulfonyl) imide and the potassium trifluoromethanesulfonate is not less than 10 mol/kg.
It should be noted that, in the electrolyte of the present application, high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate is dissolved, i.e., the molar concentration by mass is not less than 10 mol/kg; the strong solvation effect of the high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate and solvent water molecules consumes a large amount of water molecules in the electrolyte, reduces the electrochemical activity of the water molecules, inhibits the decomposition of the water molecules on the surface of an electrode, reduces the hydration effect of zinc ions, reduces the corrosion dissolution of a zinc cathode, and inhibits the zinc ions from forming zinc dendrites in the dissolution and deposition; in addition, the strong solvation effect of the high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate and solvent water molecules reduces the electrochemical activity of the water molecules, improves the electrochemical window of the electrolyte, reduces hydrogen evolution reaction and reduces zinc dissolution, and can effectively improve the cycle life of the water-system zinc ion battery.
The key point of the present application is to add a high concentration of potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate to the existing aqueous zinc ion battery electrolyte. As for the zinc salt in the aqueous zinc ion battery electrolyte, the existing aqueous zinc ion battery electrolyte can be referred to. However, in order to secure the effect of adding a high concentration of potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate, the zinc salt and its concentration, and other supporting electrolytes, functional additives, and the like that can be added are limited in the preferred embodiment of the present invention. It can be understood that the aqueous zinc ion battery electrolyte can achieve the effects of improving an electrochemical window, reducing corrosion and dissolution of zinc, inhibiting growth of zinc dendrites and improving cycle life by adding high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate; the supporting electrolyte and the functional additive may be selectively added according to different use requirements, and are not particularly limited herein.
Preferably, in the electrolyte of the present application, the mass molar concentration of the zinc salt is 0.1 to 5 mol/kg.
Preferably, in the electrolyte of the present application, the zinc salt is at least one of zinc sulfate, zinc acetate, zinc chloride, zinc nitrate, zinc perchlorate, zinc trifluoromethanesulfonate, and zinc gluconate.
The zinc salt is an important component of an aqueous zinc ion battery electrolyte, and mainly supplies zinc ions to the battery. In principle, for aqueous zinc ion battery electrolytes, it is sufficient to use water-soluble zinc salts, such as zinc sulfate, zinc acetate, zinc chloride, zinc nitrate, zinc perchlorate, zinc trifluoromethanesulfonate or zinc gluconate. The concentration of the zinc salt in the electrolyte is 0.1-5mol/kg, and enough zinc ions can be provided at the concentration; on the other hand, the high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate can enable the overall concentration of the electrolyte in the electrolyte to meet the use requirement of the battery.
Preferably, the electrolyte solution of the present application further contains a supporting electrolyte, and the supporting electrolyte is a salt of at least one of an alkali metal and an alkaline earth metal. Preferably, the salt is at least one of nitrate, sulfate, acetate and chloride.
It should be noted that the supporting electrolyte of the present application is relative to the zinc salt electrolyte, and the function of the supporting electrolyte is to utilize the electrostatic interaction between the alkali metal and alkaline earth metal cations and zinc ions to alleviate the growth of zinc dendrites, and at the same time, the introduced alkali metal and alkaline earth metal electrolyte can also be used as active ions in an aqueous zinc-alkali metal/alkaline earth metal mixed ion battery.
Preferably, the electrolyte solution of the present application further comprises a functional additive selected from at least one of polyethylene glycol, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, urea, sulfonamide and thiourea.
It should be noted that the function of the functional additive is mainly to obtain a corresponding improvement function by adding a corresponding additive, for example, the polyethylene glycol, urea, sulfonamide, thiourea and the like interact with the zinc ion empty orbit in the electrolyte through lone pair electrons provided by nitrogen, oxygen, sulfur and the like in the additive, so that the zinc ion is bound to a certain extent, the zinc ion can be slowly and uniformly deposited on the surface of the negative electrode zinc, and the zinc dendrite problem is effectively solved. Sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like are used as surfactants, and a large anionic group can form an isolating layer on the surface of the electrode to inhibit the decomposition of water and improve the working voltage.
A second aspect of the present application discloses the use of the aqueous zinc-ion battery electrolyte of the present application in a zinc-ion electrochemical energy storage device. Among them, the zinc ion electrochemical energy storage device is an electrochemical energy storage device containing zinc ions, for example, an aqueous secondary battery containing zinc ions or an aqueous battery capacitor containing zinc ions.
A third aspect of the present application discloses a zinc-ion electrochemical energy storage device employing the aqueous zinc-ion battery electrolyte of the present application.
The zinc ion electrochemical energy storage device can reduce the activity of water molecules and inhibit the decomposition of the water molecules on the surface of an electrode due to the adoption of the electrolyte; in addition, the electrochemical window of the electrolyte can be improved through strong solvation with solvent water, the working voltage of the electrochemical energy storage device is improved, and the service life is prolonged.
Preferably, the zinc ion electrochemical energy storage device of the present application is an aqueous secondary battery containing zinc ions or an aqueous battery capacitor containing zinc ions.
It can be understood that the key point of the present application is to use the aqueous zinc ion battery electrolyte of the present application, and the specific structural configuration of the electrochemical energy storage device can refer to the existing electrochemical energy storage device, such as an aqueous secondary battery containing zinc ions or an aqueous battery capacitor containing zinc ions.
Preferably, the positive electrode active material of the aqueous battery capacitor containing zinc ions of the present application uses an electric double layer porous carbon material selected from at least one of activated carbon, graphene, carbon nanotubes, and carbon fibers; the negative active material is zinc.
The aqueous battery capacitor using the positive electrode active material of the electric double layer porous carbon material is only one of the aqueous battery capacitors used in one embodiment of the present application, and does not exclude that another positive electrode active material may be used.
The beneficial effect of this application lies in:
according to the water system zinc ion battery electrolyte, due to the fact that high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate are added, strong solvation with solvent water molecules can consume a large number of water molecules in the electrolyte, electrochemical activity of the water molecules is reduced, decomposition of the water molecules on the surface of an electrode is inhibited, hydration of zinc ions is reduced, corrosion and dissolution of a zinc cathode are reduced, and zinc dendrites formed by the zinc ions in dissolution and deposition are inhibited; in addition, the strong solvation effect of the high-concentration potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate and solvent water molecules reduces the electrochemical activity of the water molecules, improves the electrochemical window of the electrolyte, reduces hydrogen evolution reaction and reduces zinc dissolution, can effectively improve the cycle life of the water-system zinc ion battery, and lays a foundation for preparing the high-quality water-system zinc ion battery.
Drawings
FIG. 1 is a topographical map of surface zinc dendrite growth after a zinc electrode in an aqueous zinc ion battery electrolyte containing 32mol/kg KFSI and 1mol/kg zinc trifluoromethanesulfonate in example one of the present application was cycled for 500 hours;
FIG. 2 is a morphology chart of surface zinc dendrite growth after a zinc electrode in an aqueous zinc ion battery electrolyte containing 1mol/kg of KFSI and 1mol/kg of zinc trifluoromethanesulfonate according to the first embodiment of the present application is circulated for 500 hours;
FIG. 3 is a graph of electrochemical window test of KFSI aqueous electrolyte of 32mol/kg and 1mol/kg by three-electrode linear sweep voltammetry in the first example of the present application, wherein the solid line is high concentration of 32mol/kgKFSI, and the dotted line is low concentration of 1mol/kg KFSI.
Detailed Description
The present application will be described in further detail with reference to specific examples. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example one
The aqueous zinc ion battery electrolyte specifically comprises solvent water, high-concentration potassium difluoride sulfonimide (KFSI) and a zinc salt, wherein the zinc salt is zinc trifluoromethanesulfonate. The preparation method comprises the following steps: KFSI is weighed according to the mass molar concentration of 32mol/kg, zinc trifluoromethanesulfonate is weighed according to the mass molar concentration of 1mol/kg, and the two are dissolved in water to obtain the aqueous zinc ion battery electrolyte with high-concentration KFSI.
In addition, for comparison, an aqueous zinc ion battery electrolyte of low-concentration potassium bis (fluorosulfonyl) imide was prepared, specifically, each component was weighed so that the molar mass concentration of KFSI was 1mol/kg and the molar mass concentration of zinc trifluoromethanesulfonate was 1mol/kg, and dissolved in water to obtain an aqueous zinc ion battery electrolyte for comparison test.
The high-concentration KFSI water-based zinc ion electrolyte and the low-concentration KFSI water-based zinc ion electrolyte of the embodiment are applied to a zinc-zinc symmetrical button cell, and 0.2mA/cm is used2The current density of the zinc sheet is charged and discharged, the time of one cycle of charging and discharging is 1 hour, and after 500 cycles, the growth condition of dendritic crystals on the surface of the zinc sheet is observed by using a mirror.
The electron microscope observation results are shown in fig. 1 and fig. 2, in which fig. 1 is a view showing the observation results of the surface of a zinc sheet using a high-concentration KFSI aqueous zinc ion electrolyte, and fig. 2 is a view showing the observation results of the surface of a zinc sheet using a low-concentration KFSI aqueous zinc ion electrolyte. The results of fig. 1 and 2 show that the zinc sheet surface using the high concentration KFSI aqueous zinc ion electrolyte is flat with no significant dendrite growth; the zinc sheet surface using the low-concentration KFSI aqueous zinc ion electrolyte used as a comparative test had many columnar dendrites.
And respectively carrying out electrochemical window test on 32mol/kg high-concentration KFSI water-based zinc ion electrolyte and 1mol/kg low-concentration KFSI water-based zinc ion electrolyte by adopting a three-electrode linear scanning voltammetry method. Wherein the working electrode and the counter electrode are Pt electrodes, the reference electrode is a saturated calomel electrode, the scanning voltage is-1.5-2V, and the scanning speed is 10 mv/s.
The test results are shown in fig. 3, in which the solid line is the test result of the high concentration KFSI aqueous zinc ion electrolyte and the dotted line is the test result of the low concentration KFSI aqueous zinc ion electrolyte. The results in fig. 3 show that the electrochemical window using the high concentration KFSI aqueous zinc ion electrolyte is 2.8V, while the electrochemical window for the comparative test low concentration KFSI aqueous zinc ion electrolyte is 2.3V.
The results in fig. 3 demonstrate that the high concentration KFSI aqueous zinc ion electrolyte has a higher voltage window; in addition, from the aspects of hydrogen evolution and oxygen evolution, in the electrolyte with high KFSI concentration, water molecules are more difficult to decompose on the surface of the electrode, and the analysis is probably caused by the strong solvation of the high KFSI concentration and solvent water molecules, so that a large amount of water molecules in the electrolyte are consumed, the activity of the water molecules is reduced, the decomposition of the water molecules on the surface of the electrode is inhibited, the corrosion and dissolution of a zinc cathode are reduced, and the growth of zinc dendrites is inhibited. In addition, the strong solvation effect of the high-concentration KFSI and solvent water molecules reduces the electrochemical activity of the water molecules, and simultaneously has the effects of improving the electrochemical window of the electrolyte, reducing hydrogen evolution reaction and reducing zinc dissolution, thereby improving the working voltage of the water system zinc ion battery.
The high-concentration KFSI water-based zinc ion electrolyte and the low-concentration KFSI water-based zinc ion electrolyte are respectively used in the water-based zinc ion battery, and the Prussian blue analogue K is adopted as the positive electrode2Zn3[Fe(CN)6]2The negative electrode adopts zinc foil, the positive electrode is uniformly mixed according to the weight ratio of active material/acetylene black/PTFE (Polytetrafluoroethylene) 80/10/10 to prepare a film, and the film is rolled on a titanium mesh and dried to prepare the electrode. Then the electrolyte and a negative electrode zinc sheet are assembled into a button cell, and the high-concentration KFSI water system zinc ion electrolyte and the low-concentration KFSI water system zinc ion electrolyte are respectively adopted as the electrolyte. The water system zinc ion battery is charged and discharged under the voltage range of 0.5-2.0V, the current density is 6A/g, and the capacity retention ratio of 3000 cycles of the water system zinc ion battery is tested.
The test result shows that the capacity retention rate of the aqueous zinc ion battery adopting the high-concentration KFSI aqueous zinc ion electrolyte is 98% after 3000 cycles, while the capacity retention rate of the aqueous zinc ion battery adopting the low-concentration KFSI aqueous zinc ion electrolyte is only 48%, which indicates that the zinc ion battery adopting the high-concentration KFSI aqueous zinc ion electrolyte has very excellent cycle stability.
Example two
The water system zinc ion battery electrolyte comprises water, high-concentration potassium trifluoromethanesulfonate and zinc salt zinc chloride, and is added with a functional additive sulfonamide, and the preparation method comprises the following steps: according to the mass molar concentration of the potassium trifluoromethanesulfonate of 20mol/kg, the mass molar concentration of the zinc chloride of 2mol/kg and the total weight ratio of the sulfamide to the electrolyte of 1.5%, weighing the components, and dissolving the components in water to obtain the aqueous zinc ion battery electrolyte of the embodiment.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that the zinc sheet using the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of this example had a smooth surface and no significant dendrite growth.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results showed that the electrochemical window of the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of this example was 2.7V.
The aqueous electrolyte of this example was used in an aqueous zinc ion battery, and Prussian blue analog K was used as the positive electrode2MnFe(CN)6The negative electrode adopts zinc foil, the positive electrode is mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 82/10/8 to prepare slurry, and the slurry is coated on stainless steel foil and dried to prepare the electrode. Then the anode, the zinc foil and the diaphragm are wound into a battery core, and the electrolyte of the water-based zinc ion battery is injected into the battery core to be packaged into a cylindrical device. The battery is charged and discharged under the voltage interval of 0.5-2.0V, the current density is 0.5A/g, and the capacity retention ratio of the battery after 1000 cycles is tested.
The test results showed that the capacity retention rate after 1000 cycles using the aqueous electrolyte solution containing 20mol/kg of potassium trifluoromethanesulfonate in this example was 90%.
EXAMPLE III
The water system zinc ion battery electrolyte comprises water, high-concentration potassium bifluoride sulfimide and zinc salt zinc perchlorate, and polyethylene glycol with the molecular weight of 300 as a functional additive, and the preparation method comprises the following steps: weighing the components according to the mass molar concentration of the potassium bis (fluorosulfonyl) imide being 20mol/kg, the mass molar concentration of the zinc perchlorate being 2mol/kg and the weight ratio of the polyethylene glycol to the total weight of the electrolyte being 1%, and dissolving the components in water to obtain the aqueous zinc ion battery electrolyte of the embodiment.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. As a result, it was found that 0.2mA/cm of the aqueous zinc ion electrolyte solution containing potassium bis (fluorosulfonylimide) at a high concentration in this example was used2After charging and discharging, and 500 times of circulation, the surface of the zinc sheet is still flat without obvious dendritic crystal growth.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results show that the electrochemical window of the high-concentration potassium bis (fluorosulfonyl) imide aqueous zinc ion electrolyte of this example is 2.6V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion hybrid capacitor, the positive electrode adopts activated carbon, the negative electrode adopts zinc foil, the positive electrode is mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 82/10/8 to prepare slurry, and the slurry is coated on stainless steel foil and dried to prepare the electrode. Then the anode and the cathode zinc foil and the diaphragm are wound into a battery core, and the aqueous electrolyte of the embodiment is injected into the battery core to be packaged into a cylindrical device. The battery is charged and discharged under the voltage range of 0.1-1.8V, the current density is 2A/g, and the capacity retention rate of 5000 cycles of the battery is tested.
The test results showed that the capacity retention rate after 5000 cycles using the aqueous electrolyte in this example was 96%.
Example four
The specific composition of the aqueous zinc ion battery electrolyte of the embodiment is water, potassium bifluorosulfonamide and zinc acetate, and potassium acetate as a supporting electrolyte is added, and the preparation method comprises the following steps: the aqueous zinc ion battery electrolyte of the present example was obtained by weighing and dissolving the components in water, with the molar mass concentration of potassium bis (fluorosulfonyl) imide being 25mol/kg, the molar mass concentration of zinc acetate being 0.5mol/kg, and the molar mass concentration of potassium acetate as a supporting electrolyte being 2 mol/kg.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. As a result, it was found that the concentration of the aqueous zinc ion electrolyte solution containing potassium bis (fluorosulfonylimide) at 0.2mA/cm was higher than that of the aqueous zinc ion electrolyte solution containing potassium bis (fluorosulfonylimide) at a concentration of potassium bis (fluorosulfonylimide) in this example2After charging and discharging, and 500 times of circulation, the zinc sheet has a flat surface and no obvious dendritic crystal growth.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results show that the electrochemical window of the high-concentration potassium bis (fluorosulfonyl) imide aqueous zinc ion electrolyte of this example is 2.7V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion hybrid capacitor, the positive electrode adopts activated carbon, the negative electrode adopts zinc foil, the positive electrode is mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 82/10/8 to prepare slurry, and the slurry is coated on graphite paper and dried to prepare the electrode. Then the film is wound with a negative electrode zinc foil and a diaphragm into a battery cell, and the water system electrolyte is injected into the battery cell to be packaged into a square soft package device. The battery is charged and discharged in a voltage range of 0.1-1.8V, the current density is 2A/g, and the capacity retention ratio of 10000 cycles of the battery is tested.
The test results showed that the capacity retention rate after 10000 cycles using the aqueous electrolyte in this example was 95%.
EXAMPLE five
The specific composition of the aqueous zinc ion battery electrolyte of the embodiment is water, potassium bis (fluorosulfonyl) imide and zinc nitrate, and a supporting electrolyte magnesium sulfate is added, and the preparation method comprises the following steps: the aqueous zinc ion battery electrolyte of the embodiment is obtained by weighing the components and dissolving the components in water according to the molar mass concentration of the potassium bis (fluorosulfonyl) imide of 28mol/kg, the molar mass concentration of the zinc nitrate of 0.5mol/kg and the molar mass concentration of the supporting electrolyte magnesium sulfate of 0.2 mol/kg.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that the aqueous zinc ion with the high concentration of potassium bis (fluorosulfonyl) imide of this example is usedZinc sheet of the sub-electrolyte at 0.2mA/cm2After charging and discharging, and 500 times of circulation, the zinc sheet has a flat surface and no obvious dendritic crystal growth.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results show that the electrochemical window of the high-concentration potassium bis (fluorosulfonyl) imide aqueous zinc ion electrolyte of this example is 2.8V.
The aqueous electrolyte of this example was used in an aqueous zinc ion battery, and Prussian blue analog K was used as the positive electrode2FeFe(CN)6The negative electrode adopts zinc foil, the positive electrode is mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 80/10/10 to prepare slurry, and the slurry is coated on graphite paper, dried and cut into electrodes. Then, the button cell is assembled with a negative zinc sheet, and the aqueous electrolyte of the embodiment is injected. The water system zinc ion battery is charged and discharged under the voltage range of 0.5-2.0V, the current density is 1A/g, and the capacity retention rate of 2000 cycles is tested.
The test results showed that the capacity retention rate after 2000 cycles using the aqueous electrolyte in this example was 82%.
EXAMPLE six
The electrolyte of the water-based zinc ion battery comprises water, potassium bifluoride sulfimide and zinc gluconate, and is added with functional additive urea, and the preparation method comprises the following steps: weighing the components according to the mass molar concentration of the potassium bis (fluorosulfonyl) imide being 25mol/kg, the mass molar concentration of the zinc gluconate being 0.3mol/kg and the urea accounting for 3% of the total weight of the electrolyte, and dissolving the components in water to obtain the aqueous zinc ion battery electrolyte.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that after the zinc sheet adopting the high-concentration potassium bis (fluorosulfonyl) imide aqueous zinc ion electrolyte of the embodiment is cycled for 500 times, the surface of the zinc sheet is smooth, and no obvious dendritic crystal grows.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results show that the electrochemical window of the high-concentration potassium bis (fluorosulfonyl) imide aqueous zinc ion electrolyte of this example is 2.7V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion battery, the positive electrode adopts lithium iron phosphate, the negative electrode adopts zinc foil, the positive electrode is mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 90/4/6 to prepare slurry, and the slurry is coated on stainless steel foil and dried to prepare the electrode. Then the anode and the cathode zinc foil and the diaphragm are wound into a battery core, and the aqueous electrolyte of the embodiment is injected into the battery core to be packaged into a cylindrical device. The battery is charged and discharged under the voltage interval of 0.5-1.5V, the current density is 0.5A/g, and the capacity retention ratio of the battery after 1000 cycles is tested.
The test results showed that the capacity retention rate of the aqueous electrolyte solution used in this example was 94% after 1000 cycles.
EXAMPLE seven
The water-based zinc ion battery electrolyte comprises water, potassium trifluoromethanesulfonate and zinc trifluoromethanesulfonate, and is added with thiourea, and the preparation method comprises the following steps: weighing the components according to the mass molar concentration of the potassium trifluoromethanesulfonate of 20mol/kg, the mass molar concentration of the zinc trifluoromethanesulfonate of 1mol/kg and the total weight ratio of the thiourea in the electrolyte of 2%, and dissolving the components in water to obtain the aqueous zinc ion battery electrolyte of the embodiment.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that after the zinc sheet adopting the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of the embodiment is cycled for 500 times, the surface of the zinc sheet is smooth, and no obvious dendritic crystal grows.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results showed that the electrochemical window of the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of this example was 2.6V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion battery, vanadium pentoxide is adopted as a positive electrode, zinc foil is adopted as a negative electrode, the positive electrode is mixed according to the weight ratio of active material/acetylene black/KS-6/PVDF (87/4/4/5) to prepare slurry, the slurry is coated on stainless steel foil, and the stainless steel foil is dried and cut into electrodes. Then, the button cell is assembled with a negative zinc sheet, and the aqueous electrolyte of the embodiment is injected. The water system zinc ion battery is charged and discharged under the voltage range of 0.1-1.6V, the current density is 1A/g, and the capacity retention ratio of 1000 cycles is tested.
The test results showed that the capacity retention rate after 1000 cycles using the aqueous electrolyte in this example was 92%.
Example eight
The specific composition of the aqueous zinc ion battery electrolyte of the embodiment is water, potassium trifluoromethanesulfonate and zinc trifluoromethanesulfonate, and the aqueous zinc ion battery electrolyte is added with sodium sulfate as a supporting electrolyte and sodium dodecyl sulfate as a functional additive, and the preparation method comprises the following steps: according to the mass molar concentration of potassium trifluoromethanesulfonate of 20mol/kg, the mass molar concentration of zinc trifluoromethanesulfonate of 0.5mol/kg, the mass molar concentration of sodium sulfate of 0.5mol/kg and the total weight ratio of sodium dodecyl sulfate to the electrolyte of 1.5%, weighing the components, and dissolving in water to obtain the aqueous zinc ion battery electrolyte of the embodiment.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that after the zinc sheet adopting the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of the embodiment is cycled for 500 times, the surface of the zinc sheet is smooth, and no obvious dendritic crystal grows.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results showed that the electrochemical window of the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of this example was 2.8V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion battery, the positive electrode adopts sodium vanadium phosphate, the negative electrode adopts zinc foil, the positive electrode is uniformly mixed according to the weight ratio of active material/acetylene black/PTFE (80/10/10) to prepare a film, and the film is rolled on a titanium mesh and dried to prepare the electrode. Then the button cell is assembled with a negative electrode zinc sheet, and the aqueous electrolyte of the embodiment is adopted as the electrolyte. The water system zinc ion battery is charged and discharged under the voltage range of 0.5-1.6V, the current density is 0.5A/g, and the capacity retention rate of 2000 cycles is tested.
The test results showed that the capacity retention of the electrolyte in the aqueous system of this example was 85% after 2000 cycles.
Example nine
The electrolyte of the water system zinc ion battery comprises water, potassium trifluoromethane sulfonate, zinc salt zinc sulfate, supporting electrolyte sodium sulfate and functional additive sodium dodecyl benzene sulfonate, and the preparation method comprises the following steps: according to the mass molar concentration of potassium trifluoromethanesulfonate of 20mol/kg, the mass molar concentration of zinc sulfate of 0.5mol/kg, the mass molar concentration of sodium sulfate of 0.5mol/kg and the total weight ratio of sodium dodecyl benzene sulfonate of 1.5 percent of the electrolyte, weighing the components, and dissolving the components in water to obtain the aqueous zinc ion battery electrolyte of the embodiment.
The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that after the zinc sheet adopting the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of the embodiment is cycled for 500 times, the surface of the zinc sheet is smooth, and no obvious dendritic crystal grows.
The electrochemical window test was performed on the aqueous zinc-ion battery electrolyte of this example using the same method as in example one. The results showed that the electrochemical window of the high-concentration potassium trifluoromethanesulfonate aqueous zinc ion electrolyte of this example was 2.7V.
The aqueous electrolyte of the embodiment is used in an aqueous zinc ion battery, the positive electrode adopts sodium vanadium phosphate, the negative electrode adopts zinc foil, the positive electrode is uniformly mixed according to the weight ratio of active material/acetylene black/PTFE (80/10/10) to prepare a film, and the film is rolled on a titanium mesh and dried to prepare the electrode. Then the button cell is assembled with a negative electrode zinc sheet, and the aqueous electrolyte of the embodiment is adopted as the electrolyte. The water system zinc ion battery is charged and discharged under the voltage range of 0.5-1.6V, the current density is 0.5A/g, and the capacity retention rate of 2000 cycles is tested.
The test results showed that the capacity retention of the electrolyte in the aqueous system of this example was 86% after 2000 cycles.
Example ten
In this example, the concentration of potassium bis (fluorosulfonyl) imide (KFSI) was adjusted based on example one, and the test was conducted by replacing part or all of potassium bis (fluorosulfonyl) imide with potassium trifluoromethanesulfonate, and the rest was the same as in example one. The formulation of the aqueous electrolyte of this example is shown in table 1.
TABLE 1 aqueous electrolyte formulations of different KFSI concentrations
| Test number | KFSI | Trifluoromethanesulfonic acid potassium salt | Zinc Trifluoromethanesulfonate (TFBS) |
| |
5mol/kg | 0mol/kg | 1mol/ |
| Test | |||
| 2 | 9mol/kg | 0mol/kg | 1mol/kg |
| Test 3 | 10mol/kg | 0mol/kg | 1mol/kg |
| Test 4 | 20mol/kg | 0mol/kg | 1mol/kg |
| Test 5 | 30mol/kg | 0mol/kg | 1mol/kg |
| Test 6 | 5mol/kg | 1mol/kg | 1mol/kg |
| Test 7 | 5mol/kg | 5mol/kg | 1mol/kg |
| Test 8 | 2mol/kg | 8mol/kg | 1mol/kg |
| Test 9 | 0mol/kg | 7mol/kg | 1mol/kg |
| Test 10 | 0mol/kg | 10mol/kg | 1mol/kg |
| Test 11 | 0mol/kg | 15mol/kg | 1mol/kg |
In this example, 11 aqueous zinc ion battery electrolytes with different concentrations were prepared according to the formulation in table 1. The dendrite growth on the surface of the zinc sheet using the electrolyte of the aqueous zinc-ion battery of this example was observed by the same method as in example. The results show that the zinc sheets using the aqueous zinc ion battery electrolytes of tests 3, 4, 5, 7, 8, 10 and 11 have smooth surfaces and no obvious dendritic crystal growth after 500 cycles; the zinc sheets using the rest of the electrolyte tested had columnar dendrites on the surface, and particularly, the zinc sheets of tests 1, 6 and 9 had obvious columnar dendrites on the surface.
Electrochemical window tests were performed on various aqueous zinc-ion battery electrolytes prepared in this example in the same manner as in example 2, and the test results are shown in table 2.
The capacity retention rate of 3000 cycles of the water-based zinc ion battery using water-based electrolytes of different concentrations was measured by the same method as in example one, and the test results are shown in table 2.
TABLE 2 electrochemical Window and Capacity Retention test results for aqueous electrolytes of varying concentrations
| Test number | Voltage window | Capacity retention rate | Test number | Voltage window | Capacity |
| Test | |||||
| 1 | 2.3V | 50％ | Test 7 | 2.7V | 92 |
| Test | |||||
| 2 | 2.4V | 65％ | Test 8 | 2.6V | 93％ |
| Test 3 | 2.6V | 91％ | Test 9 | 2.3V | 55％ |
| Test 4 | 2.7V | 94％ | Test 10 | 2.6V | 92％ |
| Test 5 | 2.8V | 98％ | Test 11 | 2.7V | 93％ |
| Test 6 | 2.3V | 51％ | / | / | / |
The results in table 1 show that the aqueous electrolyte having a concentration of 10mol/kg or more, when potassium bis (fluorosulfonyl) imide or potassium trifluoromethanesulfonate is used alone, has better cycle stability and a higher voltage window. When the potassium bis (fluorosulfonyl) imide and the potassium trifluoromethanesulfonate are used together, the total concentration of the potassium bis (fluorosulfonyl) imide and the potassium trifluoromethanesulfonate is greater than or equal to 10mol/kg, and the aqueous electrolyte also has good circulation stability and a higher voltage window.
EXAMPLE eleven
In this example, different supporting electrolytes were tested based on example four, and the rest was the same as example four. The results show that the supporting electrolyte can be used in addition to potassium acetate used in example four, other alkali or alkaline earth metal nitrates, sulfates, acetates and chlorides including lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, francium nitrate, magnesium nitrate, calcium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, francium sulfate, magnesium sulfate, calcium sulfate, lithium acetate, sodium acetate, rubidium acetate, cesium acetate, francium acetate, magnesium acetate, calcium acetate, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, magnesium chloride, calcium chloride, etc., and each supporting electrolyte is used in the same concentration as potassium acetate used in example four.
The test results show that the dendritic crystal growth condition of the zinc cathode adopting the electrolyte of different supporting electrolytes is better than that of the electrolyte without the supporting electrolyte, which indicates that the growth of the zinc dendritic crystal can be inhibited by the addition of the supporting electrolyte.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.
Claims (10)
1. An aqueous zinc ion battery electrolyte, characterized in that: the electrolyte contains water, high-concentration electrolyte salt and zinc salt;
the water is a solvent of the electrolyte, and the zinc salt is a water-soluble salt;
the high-concentration electrolyte salt is potassium bis (fluorosulfonyl) imide and/or potassium trifluoromethanesulfonate, and the molarity of the high-concentration electrolyte salt is not less than 10 mol/kg.
2. The electrolyte of claim 1, wherein: the mass molar concentration of the zinc salt is 0.1-5 mol/kg.
3. The electrolyte of claim 1, wherein: the zinc salt is at least one of zinc sulfate, zinc acetate, zinc chloride, zinc nitrate, zinc perchlorate, zinc trifluoromethanesulfonate and zinc gluconate.
4. The electrolyte of any one of claims 1 to 3, wherein: the electrolyte solution also contains a supporting electrolyte, and the supporting electrolyte is a salt of at least one of alkali metal and alkaline earth metal.
5. The electrolyte of claim 4, wherein: the salt is at least one of nitrate, sulfate, acetate and chloride.
6. The electrolyte of any one of claims 1 to 3, wherein: the electrolyte also contains a functional additive, and the functional additive is selected from at least one of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, urea, sulfonamide and thiourea.
7. Use of the electrolyte according to any one of claims 1-6 in a zinc ion electrochemical energy storage device.
8. A zinc ion electrochemical energy storage device employing the electrolyte of any one of claims 1 to 6.
9. The zinc ion electrochemical energy storage device of claim 8, wherein: the zinc ion electrochemical energy storage device is an aqueous secondary battery containing zinc ions or an aqueous battery capacitor containing zinc ions.
10. The zinc ion electrochemical energy storage device of claim 9, wherein: the positive active material of the water system battery capacitor containing zinc ions adopts an electric double layer porous carbon material, and the electric double layer porous carbon material is selected from at least one of activated carbon, graphene, carbon nano tubes and carbon fibers; the negative active material is zinc.
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