CN104882637A - Electrolyte solutions and electrochemical energy storage device - Google Patents
Electrolyte solutions and electrochemical energy storage device Download PDFInfo
- Publication number
- CN104882637A CN104882637A CN201410073028.8A CN201410073028A CN104882637A CN 104882637 A CN104882637 A CN 104882637A CN 201410073028 A CN201410073028 A CN 201410073028A CN 104882637 A CN104882637 A CN 104882637A
- Authority
- CN
- China
- Prior art keywords
- ion
- electrolyte
- metal ion
- metal
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 25
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 15
- 229940021013 electrolyte solution Drugs 0.000 title abstract 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 124
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 73
- -1 iron ions Chemical class 0.000 claims abstract description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 230000033116 oxidation-reduction process Effects 0.000 claims description 18
- 229920001940 conductive polymer Polymers 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000002322 conducting polymer Substances 0.000 claims description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 17
- 230000004888 barrier function Effects 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 230000002441 reversible effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011231 conductive filler Substances 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 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 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 229960001763 zinc sulfate Drugs 0.000 description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011883 electrode binding agent Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006388 chemical passivation reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001978 electrochemical passivation Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000006713 insertion reaction Methods 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910010908 LiM Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910003086 Ti–Pt Inorganic materials 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an aqueous electrolyte solution. The aqueous electrolyte solution comprises an electrolyte and an aqueous solution, the electrolyte solution comprises a first metal ion, and the first metal ion can reversibly deintercalate-intercalate from/to a positive electrode in the charge and discharge process; and the electrolyte solution also comprises at least one of iron ions and cerium ions. The invention also provides another aqueous electrolyte solution. The another aqueous electrolyte solution comprises the electrolyte and the aqueous solution, the electrolyte comprises the first metal ion, and the first metal ion can reversibly deintercalate and intercalate from/to the positive electrode in the charge and discharge process; and the another electrolyte solution also comprises a metal ion additive, and the redox potential of the metal ion additive is higher than the redox potential of the first metal ion in the positive electrode. The electrolyte solutions can inhibit side reactions of the positive electrode, such as conductive agent oxidation, improve the self-discharge problem of a battery, increase the capacity of the battery, and prolong the cycle life of the battery. The invention also provides an electrochemical energy storage device containing anyone of the electrolyte solutions.
Description
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of aqueous electrolyte and utilize the electrochemical energy storage device of this electrolyte.
Background technology
Lead-acid battery, its appearance is super century-old, has ripe battery technology, in occupation of the absolute market share in the energy storage fields such as automobile starting storage battery, electric bicycle, UPS.Although lead-acid battery service life cycle is lower, energy density is also relatively low, has price very cheap, the advantage that cost performance is very high.Therefore, in the last few years, Ni-MH battery, lithium ion battery, sodium-sulphur battery, flow battery etc., all cannot replace lead-acid battery in energy storage field.
There is a kind of novel water system electrochemical energy storage device in recent years.The positive pole of this energy storage device can carry out reversible deviating from-insertion reaction; Negative pole can be divided three classes, one class can carry out reversible deviating from-insertion reaction, one class to carry out reversible reduction deposition-oxidation solubilizing reaction, also has a class to be to carry out reversible adsorption-desorption reaction (this type of electrochemical energy storage device is also known as making ultracapacitor or capacitor batteries usually).The electrolyte of the type energy storage device is the aqueous solution, there is not the potential safety hazard of organic electrolyte in similar lithium ion battery, and environmentally friendly, and cost is lower, and energy density is high.Therefore, the type energy storage device promises to be the energy-storage battery of future generation of alternative lead-acid battery very much, has great using value.
But; the electrolyte of such electrochemical energy storage device is the aqueous solution; phase after charging, along with voltage raises, can there is side reaction in positive pole usually; as water in electrolyte decomposition and produce oxygen; particularly when positive pole contains carbonaceous material class conductive agent, can there is oxidation and produce carbon dioxide in carbonaceous material class conductive agent, the consumption of conductive agent makes internal resistance increase; finally affect cycle life, make such energy storage device there is self discharge problem simultaneously.These problems limit the practical application of such energy storage device, therefore urgently find effective solution.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of electrolyte, can improve self discharge problem and the cycle life of water system electrochemical energy storage device.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows: a kind of aqueous electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described electrolyte also comprises at least one in iron ion and cerium ion.
Preferably, described iron ion concentration is in the electrolytic solution not more than 5000ppm.
Preferably, described cerium ion concentration is in the electrolytic solution not more than 14010ppm.
Preferably, described first metal ion is lithium ion, sodium ion or magnesium ion.
Preferably, the pH value of described electrolyte is 3-7.
Preferably, described electrolyte also comprises sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, one or more in formate ion and alkyl sulfonate ion.
Preferably, described electrolyte also comprises the second metal ion, and described second metal ion is deposited as the second metal at cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion.
Preferably, described second metal ion is zinc ion.
Present invention also offers a kind of aqueous electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described electrolyte also comprises metal ion additive, and the oxidation-reduction potential of described metal ion additive is higher than the oxidation-reduction potential of the first metal ion in positive pole.
Present invention also offers a kind of electrochemical energy storage device, described electrochemical energy storage device comprises positive pole, negative pole and electrolyte, and described electrolyte is above-mentioned electrolyte.
Preferably, described positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion.
Preferably, described positive conductive agent comprises one or more in conducting polymer, activated carbon, Graphene, carbon black, graphite, carbon fiber.
The present invention is by adding the metal ion of actual potential near oxygen evolution potential in the electrolytic solution, the side reaction of side of the positive electrode can be suppressed, as the oxidation of carbonaceous material conductive agent produces carbon dioxide, reduce the internal resistance of cell, increase battery capacity and cycle life, improve the self discharge problem of battery, thus improve chemical property and the security performance of battery.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammogram of lithium manganate cathode.
Fig. 2 is that in electrolyte, concentration is the cyclic voltammogram of the iron ion of 1000ppm.
Fig. 3 is that in electrolyte, concentration is the cyclic voltammogram of the iron ion of 500ppm.
Fig. 4 is the discharge capacity of battery in embodiment 1 and the relation curve of internal resistance and cycle-index.
Fig. 5 is the discharge capacity of battery in embodiment 2 and the relation curve of internal resistance and cycle-index.
Fig. 6 is the discharge capacity of battery in comparative example 1 and the relation curve of internal resistance and cycle-index.
Embodiment
Clearly understand to make technical problem solved by the invention, technical scheme and beneficial effect, below in conjunction with embodiment, be further elaborated to the present invention, if be pointed out that, the concrete numerical value of the following oxidation-reduction potential related to does not illustrate, and is all relative to Zn/Zn
2+.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A kind of aqueous electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described electrolyte also comprises at least one in iron ion and cerium ion.
Electrolyte comprises electrolyte and solvent.Wherein, in electrolyte, the object of solvent dissolves electrolyte, and electrolyte is ionized in a solvent, finally generates the cation that can move freely and anion in the electrolytic solution.In the present invention, solvent is preferably the aqueous solution.
The first metal ion included in electrolyte reversiblely can be deviate from-embeds at positive pole in charge and discharge process.Namely, when battery charges, the first metal ion is deviate from from positive active material, enters electrolyte; When battery discharge, the first metal ion in electrolyte embeds in positive active material.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion.Preferred, the first metal ion is lithium ion.
Preferably, electrolyte also comprises the second metal ion, and the second metal ion is deposited as the second metal at cathodic reduction in charging process, and in discharge process, the second burning is dissolved as the second metal ion.Preferably, the second metal ion is zinc ion.
Under a preferred implementation, electrolyte comprises lithium ion and zinc ion.In charge and discharge process, lithium ion embeds at positive pole-deviates from, and zinc ion deposits at negative pole-dissolves.
At least one in iron ion and cerium ion is also comprised in electrolyte.
Solvent due to electrolyte is water, therefore phase after charging, and what comprise carbonaceous material following side reaction just very easily occurs.
H
2O→（1/2）O
2+2H
++2e
-
Normal potential: about 1.2V
C (carbon)+O
2→ CO
2+ 4e
--
Normal potential: about 1.2V
Under a preferred implementation, positive pole active material used is LiMn2O4, and conductive agent is graphite, and collector is the carbon steel being coated with PE conducting film, and the negative pole of battery is zinc electrode, and electrolyte comprises lithium ion, zinc ion and sulfate ion.Under this system, the actual potential that above-mentioned side reaction occurs is greatly about about 2.0V.And the oxidation-reduction potential of positive active material LiMn2O4 is with reference to shown in figure 1, the position of two oxidation peak, at about 1.82V and 1.94V, illustrates actual potential that side reaction the occurs oxidizing potential higher than positive active material.But when the battery phase after charging, because charge cutoff voltage is 2.1V, be easy to the above-mentioned side reactions such as the oxidation of generation carbon, thus cause the consumption of conductive agent, the internal resistance of cell increases, the problems such as cycle life shortening.
In order to solve the problem, adding iron ion or cerium ion in the electrolytic solution, can there is reversible redox reaction in iron ion or cerium ion, forms Fe
2+/ Fe
3+or Ce
3+/ Ce
4+oxidation-reduction pair, when the actual oxidation-reduction potential of iron ion or cerium ion is between the oxidation-reduction potential that oxidation-reduction potential and the side reaction of positive active material occurs, just can the phase suppress the generation of positive pole side reaction after charging, and do not affect the reaction of positive active material.
Under a preferred implementation, positive pole active material used is LiMn2O4, and conductive agent is graphite, and collector is the carbon steel being coated with PE conducting film, and the negative pole of battery is zinc electrode, and electrolyte comprises lithium ion, zinc ion and sulfate ion, also comprises iron ion.Fig. 2 and Fig. 3 is the cyclic voltammogram of the iron ion of variable concentrations, as can be seen from the figure, and Fe
2+/ Fe
3+actual oxidizing potential under this battery system is more higher than standard oxidationreduction potential value, large about about 1.95V, lower than the oxidizing potential (2.0V) of side reaction, oxidation again higher than positive active material LiMn2O4 takes off lithium current potential (1.82V and 1.94V), therefore phase after charging, while positive pole takes off lithium, also there is Fe
2+be oxidized to Fe
3+reaction, thus inhibit the generation of the side reactions such as the oxidation of carbon.
Under a preferred implementation, positive pole active material used is LiMn2O4, and conductive agent is graphite, and collector is the carbon steel being coated with PE conducting film, and the negative pole of battery is zinc electrode, and electrolyte comprises lithium ion, zinc ion and sulfate ion, also comprises cerium ion.Ce
3+/ Ce
4+actual oxidation-reduction potential also can meet requirement in the present invention, therefore also can reach the object suppressing side reaction.
Under another preferred implementation, in electrolyte, iron ion and cerium ion can also be comprised simultaneously.
Present invention also offers a kind of aqueous electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described electrolyte also comprises metal ion additive, and the oxidation-reduction potential of described metal ion additive is higher than the oxidation-reduction potential of the first metal ion in positive pole.
Preferably, described metal ion additive comprises at least one in manganese ion, lead ion, cerium ion and cobalt ions.The standard oxidationreduction potential of above-mentioned metal ion is: Mn
2+/ Mn
3+: about 1.5V, Pb
2+/ Pb
4+: about 1.62V, Ce
3+/ Ce
4+: about 1.7V and Co
2+/ Co
3+: about 1.82V.Usually the oxidation-reduction potential of these metal ion additives is higher than the oxidation-reduction potential of the first metal ion in positive active material, lower than the current potential of the above-mentioned side reaction on side of the positive electrode, therefore, it is possible to suppress the generation of side reaction.
Metal ion additive in electrolyte derives from the inorganic additive added in electrolyte, and inorganic additive can be metal simple-substance, oxide or salt, as long as be dissolved in electrolyte and generate metal ion.Metal ion additive is present in electrolyte with two kinds of valence states during discharge and recharge, forms the oxidation-reduction pair that reversible redox can occur.But when adding, the compound containing oxidation state metal element can be added, also can add the compound containing as-reduced metal element, or both add.Inorganic additive adds the method for electrolyte, according to the different situations of electrolyte or barrier film, can select different feed postition.Feed postition includes but not limited to directly add in electrolyte, or drips in the form of a solution on barrier film.Preferred, inorganic additive is directly joined in electrolyte, then electrolyte is dripped on barrier film.
In theory, as long as the concentration of iron ion or cerium ion ensures it in the electrolytic solution without Precipitation in electrolyte.But in order to reach best effect, preferably, the concentration of iron ion is not more than 5000ppm, and the concentration of cerium ion is not more than 14010ppm.Same, precipitate as long as the concentration of metal ion additive also ensures that metal ion is not separated out in the electrolytic solution.
Anion in electrolyte can be anyly substantially do not affect both positive and negative polarity reaction and the anion that dissolves in a solvent of electrolyte.Can be such as sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, formate ion, alkyl sulfonate ion and mixing thereof etc.
The concentration of each ion in electrolyte, can carry out change allotment according to different situations such as the applications of different electrolyte, solvent and battery.
Preferably, in the electrolytic solution, the concentration of the first metal ion is 0.1 ~ 10mol/L.
Preferably, in the electrolytic solution, the concentration of anion is 0.5 ~ 12mol/L.
In order to make battery performance more optimize, the pH value range of electrolyte is 3 ~ 7.The scope of pH can be adjusted by buffer.Suitable pH value both effectively can ensure capacity and the multiplying power discharging property of battery, can also avoid the problems such as electrode material corrosion.
Present invention also offers a kind of electrochemical energy storage device, comprise positive pole, negative pole and electrolyte, positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion; Electrolyte is above-mentioned electrolyte.
Positive pole comprises positive active material, and positive active material participates in positive pole reaction, and reversiblely can deviate from-embed the first metal ion.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion.Preferred, the first metal ion is lithium ion.
Preferably, positive active material has spinel structure, layer structure or olivine structural.
Positive active material can be meet general formula Li
1+xmn
ym
zo
kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn
2o
4.Preferred, positive active material contains the LiMn through overdoping or coating modification
2o
4.
Positive active material can be meet general formula Li
1+xm
ym '
zm "
co
2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO
2.
Positive active material can also be meet general formula Li
xm
1-
ym '
y(XO
4)
ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO
4.
In current battery industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn
2o
4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li
1+xmn
ym
zo
kbe as the criterion, comprise the LiMn through various modification widely
2o
4positive active material.Same, LiFePO
4and LiCoO
2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively
xm
1-ym '
y(XO
4)
nand Li
1+xm
ym '
zm "
co
2+npositive active material.
Positive active material is, when reversiblely can deviate from-embed the material of lithium ion, preferably can select as LiMn
2o
4, LiFePO
4, LiCoO
2, LiM
xpO
4, LiM
xsiO
ycompounds such as (wherein M are a kind of variable valency metal).
In addition, the compound N aVPO of sodium ion can be deviate from-embed
4f, can deviate from-embed the compound Mg M of magnesium ion
xo
y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material of battery of the present invention, therefore, the present invention is not limited to lithium ion battery.
In positive pole, use the object of conductive agent to be reduce the resistance of overall positive pole, strengthen the conductive path between positive electrode particle simultaneously.Positive conductive agent is selected from one or more in conducting polymer, activated carbon, Graphene, carbon black, graphite, carbon fiber.
In a particular embodiment; when preparing positive pole, except positive active material, conductive agent, usually also can add positive electrode binder to promote the performance of positive pole; binding agent is conducive to positive active material and conductive agent are bonded together uniformly, thus is processed to form positive pole.Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, the mixture of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates and derivative.Preferred, positive electrode binder is selected from polytetrafluoroethylene (PTFE), Kynoar (PVDF) or butadiene-styrene rubber (SBR).
Concrete, positive pole also comprises the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only as the carrier of electrical conductivity and collection, do not participate in electrochemical reaction, namely within the scope of battery operating voltage, plus plate current-collecting body can be stable be present in electrolyte and substantially side reaction do not occur, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from the one in carbon-based material, metal or alloy.
Carbon-based material is selected from the one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.
Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.
Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, carry out Passivation Treatment to plus plate current-collecting body, its main purpose is, make the surface of plus plate current-collecting body form the oxide-film of one deck passivation, thus in battery charge and discharge process, stable collection and the effect of conduction electron can be played, and cell reaction can not be participated in, ensure that battery performance is stablized.Plus plate current-collecting body deactivating process for the treatment of comprises chemical passivation process or electrochemical passivation process.
Chemical passivation process comprises by oxidizing plus plate current-collecting body, makes anode collection surface form passivating film.The principle that oxidant is selected is that oxidant can make anode collection surface form one deck passivating film and can not dissolve plus plate current-collecting body.Oxidant is selected from but is not limited only to red fuming nitric acid (RFNA) or ceric sulfate (Ce (SO
4)
2).
Electrochemical passivation process comprises and aligns pole collector and carry out electrochemical oxidation or carry out discharge and recharge process to the battery containing plus plate current-collecting body, makes anode collection surface form passivating film.
Be more preferably, positive pole also comprises the composite current collector of load positive active material, and composite current collector comprises plus plate current-collecting body and is coated on plus plate current-collecting body upper conductive film.
Conducting film to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and requirement of conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids aqueous electrolyte to the corrosion of plus plate current-collecting body.On the other hand, be conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improve the energy of battery.
Preferably, the thickness of conducting film is 10 μm ~ 2mm.
Plus plate current-collecting body has the first surface and second that are oppositely arranged, and preferably, the first surface of plus plate current-collecting body and second are all coated with conducting film.
Conducting film comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50 ~ 95%, and preferably, polymer is selected from thermoplastic polymer.In order to enable conducting film conduct electricity, there is the form that two kinds feasible: (1) polymer is conducting polymer; (2) except polymer, conducting film also comprises conductive filler.
Conducting polymer choice requirement, namely can not as the ionic conduction of charge transfer medium for having conductive capability but electrochemicaUy inert.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.Consider from the stable use electric conductivity and battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemicaUy inert, namely can not as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler mass percent scope is in the conductive film 5 ~ 50%.The average grain diameter of conductive filler is not particularly limited, and usual scope is in 100nm ~ 100 μm.
When comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer played in conjunction with conductive filler effect, and non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, polyolefin, polyamide and Kynoar is preferably.These polymer are easily melted by heat, and therefore easy and plus plate current-collecting body is combined with each other.In addition, these polymer have large potential window, thus make positive stabilizer pole be also battery output density saving in weight.Preferably, conducting film is attached on plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.
Negative pole can be divided three classes according to the difference of electrochemical energy storage device operation principle:
Under a preferred implementation, there is the embedding of reversible ion-deviate from reaction in negative side.Preferably, this ion is identical with the first metal ion in positive electrode.When the first metal ion carries out embedding and deviating from circulation time between a positive electrode and a negative electrode, form " rocking chair " battery of a kind of water system.Negative material comprises VO
2, LiV
3o
8, FeOOH, polyaniline etc.
Under a preferred implementation, there is reversible adsorption-desorption reaction in negative side.Preferably, negative material is selected from one or more porous carbon materials in active carbon, Graphene, carbon nano-tube, carbon fiber and mesoporous carbon.These materials are all carry out non-faraday's electric double layer electron adsorption process by large surface area, form mix capacitor batteries with positive pole.
Under another preferred implementation, reversible reduction deposition-oxidation solubilizing reaction can be there is in negative side.During charging, positive active material deviates from the first metal ion, there is the second metal ion in electrolyte, and the second metal ion can be reduced to the second metal in negative side, and is deposited on negative pole.During electric discharge, the second metal be deposited on negative pole is reoxidized into the second metal ion and enters in electrolyte, and the first metal ion embeds in positive active material simultaneously.Preferably, the second metal ion is zinc ion.Now, the negative material of battery, according to the difference of structure and effect, can be divided into again following three kinds of different forms:
In the first preferred embodiment, negative pole only comprises negative current collector, and negative current collector is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.
Material selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al of negative current collector or at least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or carbon-based material; Wherein, carbon-based material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90 ~ 100%.The material of negative current collector can also be selected from stainless steel or the stainless steel through Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be the stainless steel of 300 series, as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative current collector can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or at least one in oxide.The thickness range of plating/coating is 1 ~ 1000nm.Such as: tin on the negative current collector plated surface of Copper Foil or graphite foil, plumbous or silver-colored.
In the second preferred implementation, negative pole, except negative current collector, also comprises the negative electrode active material metal of load on negative current collector.
Preferably, negative electrode active material is metallic zinc.
Wherein, negative current collector with reference to the first preferred implementation, can not repeat them here.
Negative electrode active material is with sheet or Powdered existence.
When adopting the negative electrode active material of sheet, sheet metal and negative current collector form composite bed.
When adopting pulverous negative electrode active material, metal dust being made slurry, then slurry is coated on negative current collector and makes negative pole.In concrete execution mode, when preparing negative pole, except negative electrode active material metal dust, according to actual conditions, also interpolation cathode conductive agent and negative electrode binder promote the performance of negative pole as required.
In the 3rd preferred implementation, directly adopt sheet metal as negative pole, sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
In order to provide better security performance, preferably between positive pole and negative pole, be also provided with barrier film in the electrolytic solution.The short circuit that the both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes.
Barrier film does not have particular/special requirement, as long as allow electrolyte to pass through and the barrier film of electronic isolation.The various barrier films that organic system lithium ion battery adopts, all go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Below by embodiment, the present invention is further described.
Embodiment 1
Take zinc sulfate, lithium sulfate is dissolved in deionized water, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L, the pH value of electrolyte is 4.5, then adds ferrous sulfate in electrolyte, and iron concentration is 100ppm.
Embodiment 2
Be with the difference of embodiment 1: iron concentration added in electrolyte is 1000ppm, and other are all with embodiment 1.
Embodiment 3
Be with the difference of embodiment 1: iron concentration added in electrolyte is 5000ppm, and other are all with embodiment 1.
Embodiment 4
Take zinc sulfate, lithium sulfate is dissolved in deionized water, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L, the pH value of electrolyte is 4.5, then adds ceric sulfate in electrolyte, and cerium ion concentration is 100ppm.
Embodiment 5
Be with the difference of embodiment 4: cerium ion concentration added in electrolyte is 1000ppm, and other are all with embodiment 4.
Embodiment 6
Be with the difference of embodiment 4: cerium ion concentration added in electrolyte is 5000ppm, and other are all with embodiment 4.
Comparative example 1
Take zinc sulfate, lithium sulfate is dissolved in deionized water, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L, the pH value of electrolyte is 4.5.
Prepared by battery
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 86.5:1:2.5:10 in water, forms uniform anode sizing agent.Plus plate current-collecting body is the carbon steel sheet being coated with PE conducting film, thickness is 200 μm, anode sizing agent is coated on plus plate current-collecting body and forms active material layer, coating layer thickness is 350 μm, carried out compressing tablet subsequently, be cut into the pole piece of 6 × 6cm size, compacting rate is 20%, make positive pole, positive active material surface density is 750g/m
2.
Thickness is adopted to be that the zinc paper tinsel of 50 μm is as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.Electrolyte is added drop-wise to the side of barrier film, then positive pole, barrier film, negative electrode layer stacked group are dressed up battery core, the side that barrier film drips electrolyte is arranged towards negative pole; Then load in housing, be assembled into battery.
Embodiment 7-12
Embodiment 7-12 prepares battery all as stated above, unlike the electrolyte adopting embodiment 1-6 respectively.
Comparative example 2
Comparative example 2 prepares battery as stated above, and wherein electrolyte adopts the electrolyte of comparative example 1.
Performance test
Aerogenesis is tested
Battery is full of electricity, takes out anode pole piece, be placed in syringe, add electrolyte, sealing, test the gas production of every day, test gas component.Test result is in table 1, and table 1 is the gas production left standstill at 60 DEG C.
Table 1
As can be seen from Table 1, when adding iron ion in battery electrolyte, positive pole aerogenesis obtains suppression to a certain extent, and particularly when iron concentration is 1000ppm, gas production is minimum, and in gas, main component is detected as CO
2.This result shows that the electrolyte comprising iron ion provided by the invention can suppress the generation of positive pole side reaction to a certain extent, reduces the consumption of conductive agent.
Self discharge is tested
Battery in embodiment 7-12 and comparative example 2 is full of electricity, shelves three days for 60 DEG C, the remaining capacity of test battery, the current density of test is 1.4mA/
cm
2, voltage range is 1.4-2.1V, and compare testing the residual capacity obtained with the battery capacity of not shelving, the average conservation rate of the capacity that obtains, the results are shown in Table 2.Table 2 is the average conservation rate of capacity of battery after shelving three days at 60 DEG C.
As can be seen from Table 2, the battery of embodiment 7-12, the capability retention after 60 DEG C are placed is higher than the capability retention of comparative example 2 battery, illustrates and adds iron ion and cerium ion in the electrolytic solution, can improve the self discharge problem of battery, extending battery life.
Electrochemical property test
Carry out chemical property detection to the battery of embodiment 7, embodiment 8, comparative example 2 respectively, carry out constant current cycle discharge and recharge at normal temperatures with 0.2C multiplying power, voltage range is 1.4-2.1V.Fig. 4, Fig. 5 and Fig. 6 are respectively the discharge capacity of battery and the relation curve of internal resistance and cycle-index in embodiment 7, embodiment 8 and comparative example 2.In Fig. 4, the discharge capacity first of battery is about 270mAh, and circulate after 120 times, battery remaining power is approximately 220mAh, and capability retention is about 81.4%, and in Fig. 5 and Fig. 6 after circulating battery 120 times capability retention be about 83.3% and 76.6%.In addition, in Fig. 4 and Fig. 5 after circulating battery 120 times, internal resistance change is very little, and in Fig. 6, the internal resistance of battery rises more than one times after circulation 120 times.These results show, after adding iron ion and cerium ion in electrolyte, the internal resistance of battery changes less in cyclic process, and capability retention is improved.
Table 2
Although inventor has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.
Claims (16)
1. an aqueous electrolyte, comprises electrolyte and the aqueous solution, and described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; It is characterized in that: described electrolyte also comprises at least one in iron ion and cerium ion.
2. electrolyte according to claim 1, is characterized in that: described iron ion concentration is in the electrolytic solution not more than 5000ppm.
3. electrolyte according to claim 1, is characterized in that: described cerium ion concentration is in the electrolytic solution not more than 14010ppm.
4. electrolyte according to claim 1, is characterized in that: described first metal ion is lithium ion, sodium ion or magnesium ion.
5. electrolyte according to claim 1, is characterized in that: the pH value of described electrolyte is 3-7.
6. electrolyte according to claim 1, is characterized in that: described electrolyte also comprises sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, one or more in formate ion and alkyl sulfonate ion.
7. electrolyte according to claim 1, it is characterized in that: described electrolyte also comprises the second metal ion, described second metal ion is deposited as the second metal at cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion
8. electrolyte according to claim 7, is characterized in that: described second metal ion is zinc ion.
9. electrolyte according to claim 7, is characterized in that: described iron ion concentration is in the electrolytic solution not more than 5000ppm.
10. electrolyte according to claim 7, is characterized in that: described cerium ion concentration is in the electrolytic solution not more than 14010ppm.
11. electrolyte according to claim 7, is characterized in that: described first metal ion is lithium ion, sodium ion or magnesium ion.
12. electrolyte according to claim 7, is characterized in that: the pH value of described electrolyte is 3-7.
13. electrolyte according to claim 7, is characterized in that: described electrolyte also comprises sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, one or more in formate ion and alkyl sulfonate ion
14. 1 kinds of aqueous electrolytes, comprise electrolyte and the aqueous solution, and described electrolyte comprises the first metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; It is characterized in that: described electrolyte also comprises metal ion additive, the oxidation-reduction potential of described metal ion additive is higher than the oxidation-reduction potential of the first metal ion in positive pole.
15. 1 kinds of electrochemical energy storage devices, comprise positive pole, negative pole and electrolyte, and described positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion; It is characterized in that: described electrolyte is the electrolyte in claim 1-14 described in any one.
16. electrochemical energy storage devices according to claim 15, is characterized in that: described positive conductive agent comprises one or more in conducting polymer, activated carbon, Graphene, carbon black, graphite, carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410073028.8A CN104882637B (en) | 2014-02-28 | 2014-02-28 | Electrolyte and electrochemical energy storage device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410073028.8A CN104882637B (en) | 2014-02-28 | 2014-02-28 | Electrolyte and electrochemical energy storage device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104882637A true CN104882637A (en) | 2015-09-02 |
| CN104882637B CN104882637B (en) | 2021-07-13 |
Family
ID=53950035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410073028.8A Active CN104882637B (en) | 2014-02-28 | 2014-02-28 | Electrolyte and electrochemical energy storage device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104882637B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105752973A (en) * | 2016-03-31 | 2016-07-13 | 常州大学 | Method for preparing nitrogen-doped graphene material in electrochemical stripping mode |
| WO2016202276A1 (en) * | 2015-06-18 | 2016-12-22 | 苏州宝时得电动工具有限公司 | Anode material and battery |
| WO2017177960A1 (en) * | 2016-04-15 | 2017-10-19 | 苏州宝时得电动工具有限公司 | Electrolyte solution, battery, and battery pack |
| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| CN110021788A (en) * | 2018-01-09 | 2019-07-16 | 丰田自动车株式会社 | Aqueous electrolyte and aquo-lithium ion secondary cell |
| CN110190312A (en) * | 2019-06-25 | 2019-08-30 | 西安理工大学 | A kind of lead flow battery electrolyte |
| CN113013460A (en) * | 2019-12-19 | 2021-06-22 | 中国科学院大连化学物理研究所 | Negative electrolyte for alkaline zinc-iron flow battery and zinc-iron flow battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226516A (en) * | 1998-02-17 | 1999-08-25 | 北京屈臣氏蒸馏水有限公司 | Mineral water and production thereof |
| CN1348022A (en) * | 2000-10-11 | 2002-05-08 | 麦庆忠 | Electrolyte for electrothermal film of electromolding alloy |
| KR20060000822A (en) * | 2004-06-29 | 2006-01-06 | 경상대학교산학협력단 | An ambient temperature na/fes2 secondary battery |
| CN102264952A (en) * | 2008-12-26 | 2011-11-30 | 日本帕卡濑精株式会社 | Method of electrolytic ceramic coating for metal, electrolysis solution for electrolytic ceramic coating for metal, and metallic material |
| CN102332596A (en) * | 2011-08-16 | 2012-01-25 | 上海交通大学 | All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte |
| CN102586818A (en) * | 2012-03-05 | 2012-07-18 | 张家港市鹿苑电镀有限公司 | Zinc plating electrolyte |
| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
| CN103107373A (en) * | 2011-11-14 | 2013-05-15 | 苏州宝时得电动工具有限公司 | Battery |
| CN103441260A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Aqueous alkaline electrochemical energy storage device |
-
2014
- 2014-02-28 CN CN201410073028.8A patent/CN104882637B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226516A (en) * | 1998-02-17 | 1999-08-25 | 北京屈臣氏蒸馏水有限公司 | Mineral water and production thereof |
| CN1348022A (en) * | 2000-10-11 | 2002-05-08 | 麦庆忠 | Electrolyte for electrothermal film of electromolding alloy |
| KR20060000822A (en) * | 2004-06-29 | 2006-01-06 | 경상대학교산학협력단 | An ambient temperature na/fes2 secondary battery |
| CN102264952A (en) * | 2008-12-26 | 2011-11-30 | 日本帕卡濑精株式会社 | Method of electrolytic ceramic coating for metal, electrolysis solution for electrolytic ceramic coating for metal, and metallic material |
| CN102332596A (en) * | 2011-08-16 | 2012-01-25 | 上海交通大学 | All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte |
| CN103107373A (en) * | 2011-11-14 | 2013-05-15 | 苏州宝时得电动工具有限公司 | Battery |
| CN102586818A (en) * | 2012-03-05 | 2012-07-18 | 张家港市鹿苑电镀有限公司 | Zinc plating electrolyte |
| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
| CN103441260A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Aqueous alkaline electrochemical energy storage device |
Non-Patent Citations (1)
| Title |
|---|
| FRITZ BECK ET AL.: "Rechargeable batteries with aqueous electrolytes", 《ELECTROCHIMICA ACTA》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016202276A1 (en) * | 2015-06-18 | 2016-12-22 | 苏州宝时得电动工具有限公司 | Anode material and battery |
| CN105752973A (en) * | 2016-03-31 | 2016-07-13 | 常州大学 | Method for preparing nitrogen-doped graphene material in electrochemical stripping mode |
| WO2017177960A1 (en) * | 2016-04-15 | 2017-10-19 | 苏州宝时得电动工具有限公司 | Electrolyte solution, battery, and battery pack |
| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| CN110021788A (en) * | 2018-01-09 | 2019-07-16 | 丰田自动车株式会社 | Aqueous electrolyte and aquo-lithium ion secondary cell |
| JP2019121537A (en) * | 2018-01-09 | 2019-07-22 | トヨタ自動車株式会社 | Aqueous electrolyte solution and aqueous lithium ion secondary battery |
| US11211640B2 (en) | 2018-01-09 | 2021-12-28 | Toyota Jidosha Kabushiki Kaisha | Aqueous electrolyte solution, and aqueous lithium ion secondary battery |
| CN110021788B (en) * | 2018-01-09 | 2022-08-12 | 丰田自动车株式会社 | Aqueous electrolyte and aqueous lithium ion secondary battery |
| CN110190312A (en) * | 2019-06-25 | 2019-08-30 | 西安理工大学 | A kind of lead flow battery electrolyte |
| CN110190312B (en) * | 2019-06-25 | 2021-01-15 | 西安理工大学 | Electrolyte for lead flow battery |
| CN113013460A (en) * | 2019-12-19 | 2021-06-22 | 中国科学院大连化学物理研究所 | Negative electrolyte for alkaline zinc-iron flow battery and zinc-iron flow battery |
| CN113013460B (en) * | 2019-12-19 | 2022-06-14 | 中国科学院大连化学物理研究所 | Negative electrolyte for alkaline zinc-iron flow battery and zinc-iron flow battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104882637B (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104882637A (en) | Electrolyte solutions and electrochemical energy storage device | |
| CN105336993A (en) | Electrolyte solution and battery | |
| CN103107373B (en) | Battery | |
| WO2017020860A1 (en) | Battery, battery set and uninterruptable power source | |
| CN104766971B (en) | Positive electrode, the water system battery containing positive electrode | |
| CN104733785B (en) | Battery | |
| US10522869B2 (en) | Battery, battery pack, and uninterruptible power supply | |
| CN106549189A (en) | Battery, set of cells and uninterrupted power source | |
| CN104752681A (en) | Battery | |
| CN104766994A (en) | Battery | |
| CN106374145A (en) | Colloidal electrolyte and battery containing colloidal electrolyte | |
| CN106328950A (en) | Positive electrode material and battery | |
| CN104518205A (en) | Preparation method for zinc anode, zinc anode and battery | |
| CN103094627A (en) | Battery | |
| CN105742637A (en) | Positive material and battery containing same | |
| CN106207242A (en) | Aqueous electrolyte and battery | |
| TW202111729A (en) | Electrolyte solution, battery and battery pack | |
| CN104733787B (en) | Battery | |
| CN109119635B (en) | Battery with a battery cell | |
| CN105449294A (en) | Battery | |
| CN104282910A (en) | Battery | |
| CN104282952A (en) | Electrolyte and battery | |
| CN108666575A (en) | Combined conductive agent and preparation method thereof, Anode and battery | |
| CN105336956A (en) | Battery | |
| WO2016202276A1 (en) | Anode material and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240531 Address after: No.1 Loushan Road, Loushan Street, Licang District, Qingdao City, Shandong Province Patentee after: Ruihai Po (Qingdao) Energy Technology Co.,Ltd. Country or region after: China Address before: 215123 Jiangsu Province, Suzhou City Industrial Park East Road, No. 18 Patentee before: POSITEC POWER TOOLS (SUZHOU) Co.,Ltd. Country or region before: China Patentee before: Chen Pu Country or region before: Canada |