CN110120309B - Aqueous electrolyte and application thereof - Google Patents
Aqueous electrolyte and application thereof Download PDFInfo
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- CN110120309B CN110120309B CN201910439531.3A CN201910439531A CN110120309B CN 110120309 B CN110120309 B CN 110120309B CN 201910439531 A CN201910439531 A CN 201910439531A CN 110120309 B CN110120309 B CN 110120309B
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- aqueous electrolyte
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- nitrate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical group [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims abstract description 37
- 239000004304 potassium nitrite Substances 0.000 claims abstract description 37
- 235000010289 potassium nitrite Nutrition 0.000 claims abstract description 37
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 11
- 235000010344 sodium nitrate Nutrition 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 4
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 claims description 4
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 3
- SIONIIVXRCVHFL-UHFFFAOYSA-N benzyl 3-[(2-methylpropan-2-yl)oxycarbonylamino]piperidine-1-carboxylate Chemical compound C1C(NC(=O)OC(C)(C)C)CCCN1C(=O)OCC1=CC=CC=C1 SIONIIVXRCVHFL-UHFFFAOYSA-N 0.000 claims description 3
- KTTSJTVLWUJJMN-UHFFFAOYSA-L cadmium(2+);dichlorate Chemical compound [Cd+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O KTTSJTVLWUJJMN-UHFFFAOYSA-L 0.000 claims description 3
- IQYVXTLKMOTJKI-UHFFFAOYSA-L cobalt(ii) chlorate Chemical compound [Co+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IQYVXTLKMOTJKI-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 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 claims description 2
- 239000003990 capacitor Substances 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000011056 performance test Methods 0.000 description 5
- 238000004832 voltammetry Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940104869 fluorosilicate Drugs 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229910002548 FeFe Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 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
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000358 iron sulfate 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
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a water system electrolyte, which comprises a limited domain water molecule functional solute, water and electrolyte; the limited water molecule functional solute is potassium nitrite, and the mass percentage of the limited water molecule functional solute in the water system electrolyte is more than 50%; the electrolyte is soluble salt or soluble hydroxide of alkali metal and/or alkaline earth metal. The aqueous electrolyte has a high voltage window and a wide working temperature range, and is suitable for a high-voltage low-temperature-resistant aqueous hybrid supercapacitor. The invention also discloses application of the aqueous electrolyte and an electrochemical energy storage device containing the aqueous electrolyte.
Description
Technical Field
The present invention relates to the field of electrochemical energy storage. More particularly, to an aqueous electrolyte and its use.
Background
The super capacitor is an electrochemical energy storage device between a traditional capacitor and a secondary battery, and has wide application in the fields of intelligent instruments, new energy vehicles, military high-power supplies and the like. The super capacitor has ultrahigh power density which is more than tens times of that of the secondary battery; the service life is very long, and can reach more than 50 ten thousand cycle life and more than ten years calendar life; however, the super capacitor also has the disadvantage of low energy density, which restricts the development and application thereof. In order to increase the energy storage density of the super capacitor, researchers usually work on both developing high specific volume electrode materials and increasing the operating voltage of the device.
The working voltage of the device is improved, and the super capacitor can also play a significant role in improving the energy density of the super capacitor. From the capacitive storage calculation formula E ═ CU2And 2, the energy storage of the super capacitor can be obviously improved by increasing the working voltage U. The working voltage of the super capacitor is mainly determined by the electrochemical stability window of the electrolyte and the matching performance between the electrolyte and the electrode material. The electrolyte of the super capacitor generally comprises a water-based electrolyte and an organic electrolyte. The aqueous solution system electrolyte is the electrolyte which is applied to the super capacitor at the earliest time, and has the main advantages of high conductivity, effective reduction of internal resistance of a device, small electrolyte molecule diameter, easy full infiltration with micropores, convenient full utilization of surface area and low price. However, the conventional aqueous electrolyte is limited by low decomposition voltage (1.23V) of water, small electrochemical window, and strong acid or strong alkali has strong corrosivity, so that the packaging requirement is severe and the operation is not facilitated. At present, most of commercial super capacitors adopt organic system electrolyte, and the working voltage of the super capacitor adopting the organic system electrolyte to replace water system electrolyte can be improved from 0.9V to 2.5-2.7V. The electrolyte salt commonly used in the organic electrolyte generally adopts quaternary ammonium salt, the production cost is high, and the adopted organic solvent is inflammable and safeThe integrity is poor.
In comparison, the aqueous electrolyte has the advantages of lower impedance, high power, environmental protection, safety and the like, but due to a smaller electrochemical stable voltage window, the commercial application in the field of supercapacitors is behind that of an organic system. Inspiring breakthrough in the research on high-voltage aqueous electrolytes in recent years, the discovery of Suo et al was reported in the journal of Science (Science,2015,350,938.) by the end of 2015, and the water-in-salt system proposed by the invention can greatly improve the electrochemical window of the electrolytes, indicating that the aqueous electrolytes are expected to obtain a working voltage close to that of organic systems. However, the method still faces the problems of high cost, poor interface compatibility, poor high pressure resistance, poor low temperature resistance and the like.
Disclosure of Invention
The first object of the present invention is to provide an aqueous electrolyte solution having a high voltage window and a wide operating temperature range and suitable for use in an aqueous hybrid supercapacitor having high voltage and low temperature resistance.
A second object of the present invention is to provide the use of an aqueous electrolyte as provided in the first object above in an electrochemical energy storage device.
A third object of the present invention is to provide an electrochemical energy storage device.
In order to achieve the first purpose, the invention adopts the following technical scheme:
an aqueous electrolyte comprises a limited water molecule functional solute, water and electrolyte; wherein,
the limited water molecule functional solute is potassium nitrite, and the mass percentage of the limited water molecule functional solute in the water system electrolyte is more than 50%;
the electrolyte is soluble salt or soluble hydroxide of alkali metal and/or alkaline earth metal.
It should be noted that the limited water molecule functional solute and the electrolyte are chosen differently.
Researches show that potassium nitrite limited domain water molecule functional solute with the mass percentage content of more than 50 percent is added into water system electrolyte, and through the interaction of the high-concentration limited domain water molecule functional solute and water molecules in the electrolyte, almost all water molecules in the electrolyte are tightly connected with anions and cations of the limited domain water molecule functional solute through Van der Waals force, so that the electrolysis of the water molecules on the surface of an electrode is inhibited; in addition, due to the fact that almost no free water molecules exist, hydrogen bonds in the water system electrolyte are reduced rapidly, so that the freezing point of the water system electrolyte is greatly reduced, the working temperature of the electrolyte is widened (the tolerant temperature range is-40-60 ℃), the voltage window (not lower than 2.5V) is improved, the capacity retention rate and the service life of an electrochemical energy storage device are improved, and the electrochemical performance of the electrochemical energy storage device is greatly improved.
Optionally, the mass percentage of the limited water molecule functional solute in the aqueous electrolyte is 55-80%, preferably 60-80%.
Optionally, the aqueous electrolyte further comprises an auxiliary agent, and the auxiliary agent is selected from one or more of ammonium nitrate, ammonium thiocyanate, silver perchlorate, zinc iodide, lead fluosilicate, ammonium iodide, cadmium chlorate, mercurous perchlorate, cobalt chlorate, manganese nitrate, ferrous perchlorate, ferric sulfate, copper chlorate and zinc fluoride. The existence of the auxiliary agent further improves the voltage window of the aqueous electrolyte and widens the working temperature range of the aqueous electrolyte.
Optionally, the mass percentage of the auxiliary agent in the aqueous electrolyte is 1-25%.
Optionally, the mass percentage of the electrolyte in the aqueous electrolyte is 1-35%.
Optionally, the soluble salt of an alkali metal and/or an alkaline earth metal is selected from the group consisting of sulfates, nitrates, acetates and chlorides of an alkali metal and/or an alkaline earth metal.
Optionally, the soluble salt of the alkali metal is selected from one or more of lithium sulfate, lithium nitrate, lithium acetate, lithium chloride, sodium sulfate, sodium nitrate, sodium acetate, sodium chloride, potassium sulfate, potassium nitrate, potassium acetate and potassium chloride.
Optionally, the soluble salt of the alkaline earth metal is selected from one or more of magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, calcium nitrate, calcium acetate, calcium chloride, strontium nitrate, strontium acetate, strontium chloride, barium nitrate, barium acetate and barium chloride.
Optionally, the soluble hydroxide of the alkali metal is selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
The water system electrolyte can be prepared by dissolving the limited water molecule functional solute, the auxiliary agent and the electrolyte in water according to a certain chemical dose ratio and dissolving the limited water molecule functional solute, the auxiliary agent and the electrolyte in a magnetic stirring and/or heating mode.
In order to achieve the second object, the present invention also provides the use of the aqueous electrolyte as described above in an electrochemical energy storage device.
In order to achieve the third object, the present invention further provides an electrochemical energy storage device, which comprises the above-mentioned aqueous electrolyte.
Optionally, the electrochemical energy storage device is an aqueous secondary battery or an aqueous electrochemical supercapacitor or an organic combination of both.
Optionally, the water-based secondary battery is selected from one or more of a water-based lithium ion battery, a sodium ion battery, a potassium ion battery and a zinc ion battery.
The invention has the following beneficial effects:
the water system electrolyte provided by the invention has a high voltage window and a wide working temperature range, and is suitable for a high-voltage low-temperature-resistant water system hybrid supercapacitor. In the application and the electrochemical energy storage device provided by the invention, the aqueous electrolyte is adopted, so that the decomposition voltage of the electrolyte is improved, the working temperature is widened, the electrochemical performance and the application range of the electrochemical energy storage device are further improved, and a foundation is laid for the popularization and the application of the electrochemical energy storage device.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows the cycle performance test results obtained in the aqueous lithium ion supercapacitor to be prepared in example 1.
Fig. 2 shows the cycle performance test results obtained in the aqueous lithium ion supercapacitor to be prepared in example 3.
Fig. 3 shows the cycle performance test results obtained in the aqueous lithium ion supercapacitor prepared in example 6.
Fig. 4 shows the cycle performance test results obtained in the aqueous lithium ion supercapacitor prepared in example 10.
Fig. 5 shows the cycle performance test results obtained in the aqueous lithium ion supercapacitor prepared in example 15.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The water system electrolyte of the embodiment specifically comprises solvent water, limited water molecule functional solute is potassium nitrite, and electrolyte is sodium nitrate, and the preparation method comprises the following steps: the components were weighed out in a weight ratio of water/potassium nitrite/sodium nitrate of 1/3/0.1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the mass fraction of the potassium nitrite in the electrolyte is 73.2%. The electrochemical window of the water system electrolyte prepared in the embodiment is tested by adopting a three-electrode linear voltammetry, a saturated calomel electrode is taken as a reference electrode, a platinum disk electrode is taken as a counter electrode and a working electrode, the electrochemical stability window of the water system electrolyte is measured to reach 2.7V by adopting a linear scanning voltammetry, and the water system electrolyte can stably work at the temperature of minus 40 ℃.
The aqueous electrolyte of this example was used in an aqueous sodium ion supercapacitor, and the positive electrode and the negative electrode were each Na2FeFe(CN)6And commercialized active carbon, the positive negative pole is according to the active material/acetylene black/PTFE 7/2/1 weight ratio mixes and makes the thick liquids, and coat on the graphite paper, make the electrode after oven drying. And then assembled into a super capacitor, wherein the diaphragm is the diaphragm of a commercial nickel-metal hydride battery, and the electrolyte is the water-based electrolyte in the embodiment. At 0-2.0VThe charge and discharge test was carried out, the current density was 1A/g, the capacity retention rate was 92% after 2000 cycles at room temperature, and the results are shown in FIG. 1.
Example 2
The water system electrolyte of the embodiment specifically comprises solvent water, limited water molecule functional solute is potassium nitrite, and the electrolyte is potassium nitrate, and the preparation method comprises the following steps: the components were weighed out in a weight ratio of water/potassium nitrite/potassium nitrate of 1/3/0.1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the mass fraction of the potassium nitrite in the electrolyte is 73.2%. The electrochemical window of the aqueous electrolyte prepared in the embodiment is tested by adopting a three-electrode linear voltammetry, the electrochemical stability window of the aqueous electrolyte reaches 2.9V, and the aqueous electrolyte can stably work at-40 ℃.
The aqueous electrolyte of this example was used in an aqueous potassium supercapacitor, and the positive electrode and the negative electrode were each K2FeFe(CN)6And commercialized active carbon, the positive negative pole is according to the active material/acetylene black/PTFE 8/1/1 weight ratio mixes and makes the thick liquids, and coat on the graphite paper, make the electrode after oven drying. And then assembled into a super capacitor, wherein the diaphragm is the diaphragm of a commercial nickel-metal hydride battery, and the electrolyte is the water-based electrolyte in the embodiment. The charge and discharge test is carried out at 0-2.0V, the current density is 1A/g, the capacity retention rate is 90 percent after the cycle is carried out for 2000 times at room temperature.
Example 3
The water system electrolyte of the embodiment specifically comprises solvent water, limited water molecule functional solute is potassium nitrite, and the electrolyte is potassium hydroxide, and the preparation method comprises the following steps: the components were weighed out in a weight ratio of water/potassium nitrite/potassium hydroxide of 1/3/0.3, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the mass fraction of the potassium nitrite in the electrolyte is 69.7%. The electrochemical window of the aqueous electrolyte prepared in the embodiment is tested by adopting a three-electrode linear voltammetry, the electrochemical stability window of the aqueous electrolyte reaches 2.8V, and the aqueous electrolyte can stably work at-40 ℃.
The aqueous electrolyte of the example is used in an aqueous symmetrical double-layer supercapacitor, the positive electrode and the negative electrode are both commercialized activated carbon, the positive electrode and the negative electrode are mixed according to the weight ratio of active material/acetylene black/PTFE (8/1/1) to prepare slurry, and the slurry is coated on graphite paper and dried to prepare the electrode. And then assembled into a super capacitor, wherein the diaphragm is the diaphragm of a commercial nickel-metal hydride battery, and the electrolyte is the water-based electrolyte in the embodiment. The charge and discharge test was carried out at 0-2V, the current density was 1A/g, the capacity retention rate was 92% after 4000 cycles at room temperature, and the results are shown in FIG. 2.
Example 4
The water system electrolyte of the embodiment specifically comprises solvent water, limited water molecule functional solute is potassium nitrite, and the electrolyte is lithium acetate, and the preparation method comprises the following steps: the components were weighed out in a weight ratio of water/potassium nitrite/lithium acetate of 1/3/0.3, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the mass fraction of the potassium nitrite in the electrolyte is 69.7%. The electrochemical window of the aqueous electrolyte prepared in the embodiment is tested by adopting a three-electrode linear voltammetry, the electrochemical stability window of the aqueous electrolyte reaches 2.7V, and the aqueous electrolyte can stably work at-40 ℃.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion super capacitor, the positive electrode and the negative electrode are respectively commercialized lithium manganate and activated carbon, the positive electrode and the negative electrode are mixed according to the weight ratio of active material/acetylene black/PVDF (polyvinylidene fluoride) 8/1/1 to prepare slurry, and the slurry is coated on a carbon-coated aluminum foil and dried to prepare the electrode. And then assembled into a super capacitor, wherein the diaphragm is the diaphragm of a commercial nickel-metal hydride battery, and the electrolyte is the water-based electrolyte in the embodiment. The charge and discharge test is carried out under 0-2V, the current density is 1A/g, the capacity retention rate is 92 percent after 4000 cycles at room temperature.
Example 5
Example 1 was repeated except that the aqueous electrolyte further contained an auxiliary agent ammonium nitrate, and the weight ratio of each component was 1/3/0.5/0.1, where potassium nitrite was 65.2% by mass of the electrolyte, and the remaining conditions were unchanged, the electrochemical stability window of the aqueous electrolyte reached 2.9V, and the minimum operating temperature was-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% after 2000 cycles at room temperature.
Example 6
Example 1 was repeated except that the aqueous electrolyte further included an auxiliary agent of silver perchlorate, and the weight ratio of the components was water/potassium nitrite/silver perchlorate/sodium nitrate was 1/3/0.4/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 66.7%, and the rest conditions were unchanged, and the obtained aqueous electrolyte had an electrochemical stability window of 3.0V and a minimum operating temperature of-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery according to the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the current density was 1A/g, and the capacity retention ratio was 93% when the battery was cycled 3000 times at room temperature, as shown in fig. 3.
Example 7
Example 1 was repeated except that the aqueous electrolyte further contained an auxiliary agent of lead fluorosilicate, and the weight ratio of each component was water/potassium nitrite/lead fluorosilicate/sodium nitrate was 1/3/0.3/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 68.2%, and the remaining conditions were unchanged, and the obtained aqueous electrolyte had an electrochemical stability window of 3.0V and a minimum operating temperature of-42 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 91% after 2000 cycles at room temperature.
Example 8
Example 1 was repeated except that the aqueous electrolyte further contained an auxiliary agent ammonium thiocyanate, and the weight ratio of the components was water/potassium nitrite/lead fluorosilicate/sodium nitrate was 1/3/0.5/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 65.2%, and the remaining conditions were unchanged, and the obtained aqueous electrolyte had an electrochemical stability window of 2.9V and a minimum operating temperature of-41 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 91% after 2000 cycles at room temperature.
Example 9
Example 3 was repeated except that the aqueous electrolyte further contained an auxiliary ammonium iodide, and the weight ratio of the components was water/potassium nitrite/ammonium iodide/sodium nitrate was 1/3/0.5/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 65.2%, and the remaining conditions were unchanged, and the obtained aqueous electrolyte had an electrochemical stability window of 2.9V and a minimum operating temperature of-45 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, with a current density of 1A/g, and a capacity retention rate of 95% after 8000 cycles at room temperature.
Example 10
Example 3 was repeated except that the aqueous electrolyte further contained an auxiliary agent of cadmium chlorate, and the weight ratio of the components was 1/3/0.1/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 71.4%, and the other conditions were unchanged, the electrochemical stability window of the obtained aqueous electrolyte reached 3.0V, and the minimum operating temperature was-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery according to the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the current density was 1A/g, and the capacity retention rate was 92% when the battery was cycled 2000 times at room temperature, and the results are shown in fig. 4.
Example 11
Example 3 is repeated, except that the water-based electrolyte further comprises an auxiliary agent of mercurous perchlorate, the weight ratio of the components is 1/3/0.5/0.1, wherein the mass fraction of potassium nitrite in the electrolyte is 65.2%, the rest conditions are unchanged, the electrochemical stability window of the obtained water-based electrolyte reaches 2.9V, and the minimum working temperature is-45 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, with a current density of 1A/g, and with a capacity retention rate of 96% after 2000 cycles at room temperature.
Example 12
Example 3 was repeated except that the aqueous electrolyte further contained an auxiliary agent cobalt chlorate, and the weight ratio of each component was 1/3/0.4/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 66.6%, and the remaining conditions were unchanged, and the electrochemical stability window of the obtained aqueous electrolyte reached 2.9V, and the minimum operating temperature was-44 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% after 2000 cycles at room temperature.
Example 13
Example 3 was repeated except that the aqueous electrolyte further contained an auxiliary agent manganese nitrate, and the weight ratio of each component was 1/3/0.2/0.1, where potassium nitrite was 69.8% by mass of the electrolyte, and the remaining conditions were unchanged, the electrochemical stability window of the aqueous electrolyte reached 2.9V, and the minimum operating temperature was-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% after 2000 cycles at room temperature.
Example 14
Example 3 is repeated, except that the water-based electrolyte further comprises an auxiliary agent of ferrous perchlorate, the weight ratio of the components is water/potassium nitrite/ferrous perchlorate/sodium nitrate is 1/3/0.6/0.1, wherein the mass fraction of potassium nitrite in the electrolyte is 63.8%, the rest conditions are unchanged, the electrochemical stability window of the obtained water-based electrolyte reaches 2.8V, and the minimum working temperature is-41 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 91% after 2000 cycles at room temperature.
Example 15
Example 3 was repeated, except that the aqueous electrolyte further included an auxiliary agent of copper chlorate, and the weight ratio of each component was water/potassium nitrite/copper chlorate/sodium nitrate was 1/3/0.5/0.1, wherein the mass fraction of potassium nitrite in the electrolyte was 65.2%, and the rest conditions were unchanged, and the obtained aqueous electrolyte had an electrochemical stability window of 2.9V and a minimum operating temperature of-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery according to the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, the current density was 1A/g, the capacity retention rate was 92% after cycling at room temperature 10000 times, and the results are shown in fig. 5.
Example 16
Example 3 was repeated except that the aqueous electrolyte further contained an auxiliary agent of iron sulfate, and the weight ratio of the components was 1/3/0.5/0.1, where potassium nitrite was 65.2% by mass of the electrolyte, and the remaining conditions were unchanged, the electrochemical stability window of the aqueous electrolyte reached 2.9V, and the minimum operating temperature was-43 ℃.
The aqueous electrolyte was used in an aqueous sodium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0 to 2.0V, with a current density of 1A/g, and with a capacity retention rate of 90% after 2000 cycles at room temperature.
Comparative example 1
Example 1 was repeated except that the aqueous electrolyte was prepared by changing the limited water molecule functional solute potassium nitrite to potassium chloride with the remaining conditions unchanged, the electrochemical stability window of the aqueous electrolyte reached 2.5V, and the battery discharge capacity rapidly declined below 22% of the battery capacity at room temperature when the temperature was below-35 ℃.
Comparative example 2
Example 1 was repeated except that the aqueous electrolyte was prepared by changing the composition of the aqueous electrolyte to 1/0.9/0.1 by weight ratio of water/potassium nitrite/sodium nitrate, that is, the mass fraction of potassium nitrite in the electrolyte was 45%, and the remaining conditions were not changed, and the electrochemical stability window of the aqueous electrolyte reached 2.6V, and when operated at-40 ℃, the battery discharge capacity rapidly declined to less than 16% of the battery capacity at room temperature.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (8)
1. The water system electrolyte is characterized by comprising a limited water molecule functional solute, water and an electrolyte, or comprising the limited water molecule functional solute, the water, the electrolyte and an auxiliary agent; wherein,
the limited water molecule functional solute is potassium nitrite, and the mass percentage of the limited water molecule functional solute in the water system electrolyte is more than 50%;
the electrolyte is soluble salt or soluble hydroxide of alkali metal and/or alkaline earth metal;
the auxiliary agent is selected from one or more of ammonium nitrate, ammonium thiocyanate, silver perchlorate, zinc iodide, lead fluosilicate, ammonium iodide, cadmium chlorate, mercurous perchlorate, cobalt chlorate, manganese nitrate, ferrous perchlorate, ferric sulfate, copper chlorate and zinc fluoride; wherein the mass percentage of the auxiliary agent in the aqueous electrolyte is 1-25%.
2. The aqueous electrolyte solution according to claim 1, wherein the electrolyte is contained in the aqueous electrolyte solution in an amount of 1 to 35% by mass.
3. The aqueous electrolyte as claimed in claim 1, characterized in that the soluble salts of alkali metals and/or alkaline earth metals are selected from the group consisting of sulfates, nitrates, acetates and chlorides of alkali metals and/or alkaline earth metals.
4. The aqueous electrolyte of claim 1, wherein the soluble salt of an alkali metal is selected from one or more of lithium sulfate, lithium nitrate, lithium acetate, lithium chloride, sodium sulfate, sodium nitrate, sodium acetate, sodium chloride, potassium sulfate, potassium nitrate, potassium acetate, and potassium chloride; the soluble salt of the alkaline earth metal is selected from one or more of magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, calcium nitrate, calcium acetate, calcium chloride, strontium nitrate, strontium acetate, strontium chloride, barium nitrate, barium acetate and barium chloride.
5. Use of an aqueous electrolyte according to any of claims 1 to 4 in an electrochemical energy storage device.
6. An electrochemical energy storage device comprising an aqueous electrolyte according to any one of claims 1 to 4.
7. An electrochemical energy storage device as in claim 6, wherein said electrochemical energy storage device is an aqueous secondary battery or an aqueous electrochemical supercapacitor or an organic combination of both.
8. An electrochemical energy storage device as in claim 7, wherein said aqueous secondary battery is selected from one or more of aqueous lithium ion batteries, sodium ion batteries, potassium ion batteries and zinc ion batteries.
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