CN110767927A - Electrolyte for static zinc-bromine liquid battery - Google Patents
Electrolyte for static zinc-bromine liquid battery Download PDFInfo
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- CN110767927A CN110767927A CN201911031712.9A CN201911031712A CN110767927A CN 110767927 A CN110767927 A CN 110767927A CN 201911031712 A CN201911031712 A CN 201911031712A CN 110767927 A CN110767927 A CN 110767927A
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- bromide
- bromine
- battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 230000003068 static effect Effects 0.000 title claims abstract description 37
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 66
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 33
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 20
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 210000001787 dendrite Anatomy 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 12
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 30
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-methylmorpholine Substances CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- -1 1-butyl-2, 3-dimethylpyridine bromide Chemical compound 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- LKYKNKAPCZIXRF-UHFFFAOYSA-N CCN1C=CC=C(C)C1.Br Chemical compound CCN1C=CC=C(C)C1.Br LKYKNKAPCZIXRF-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- FCGQIZKUTMUWDC-UHFFFAOYSA-M trimethyl(propyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)C FCGQIZKUTMUWDC-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 10
- 239000011701 zinc Substances 0.000 abstract description 10
- 238000007599 discharging Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 208000012868 Overgrowth Diseases 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 52
- 239000007864 aqueous solution Substances 0.000 description 33
- 239000001103 potassium chloride Substances 0.000 description 26
- 235000011164 potassium chloride Nutrition 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 9
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WZXMNMMHNCFXLH-UHFFFAOYSA-N CCN1C=CC=CC1C.Br Chemical compound CCN1C=CC=CC1C.Br WZXMNMMHNCFXLH-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention provides an electrolyte for a static zinc-bromine liquid battery, which mainly comprises zinc bromide, a bromine complexing agent, a dendrite inhibitor, a conductive agent, a pH regulator and distilled water. According to the electrolyte for the static zinc-bromine liquid battery, the dendritic crystal inhibitor and the bromine complexing agent are added, and the pH value of the electrolyte is adjusted through the pH regulator, so that on one hand, the overgrowth of Zn crystal grains in the charging process can be effectively inhibited, the continuous and stable current in the charging and discharging process is kept, the energy efficiency and the cycle life of the battery are greatly improved under the condition of ensuring the reduction of the cost of the electrolyte, on the other hand, the self-discharging process of the zinc-bromine battery can be effectively inhibited, the static battery manufacturing is realized, the cycle process of the electrolyte is avoided, when the electrolyte is used for a battery system, a cycle device can be removed, the structure of the liquid battery is simplified, and the manufacturing process difficulty and the cost of the battery are greatly reduced.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to electrolyte for a static zinc-bromine liquid battery.
Background
With the gradual depletion of fossil energy such as petroleum, coal and the like, uneven distribution of geographic positions and continuously aggravated environmental pollution, the energy crisis and environmental pressure become increasingly severe; the storage technology of renewable energy effectively alleviates these problems and gradually becomes the main development direction of energy.
The flow battery is a novel chemical energy storage device. The electrochemical flow battery, namely the redox battery, has the characteristics of high efficiency, environmental protection, capability of large-current charge and discharge, deep discharge and the like, the battery capacity is related to the volume of battery electrolyte and the concentration of battery active materials, and the design has certain flexibility. The zinc bromine liquid battery is used as a combination of a flow battery technology and an energy storage technology, and has a very high application prospect in the field of energy storage.
Zinc-bromine liquid batteries are a single deposition type electrochemical system that stores energy in solution. When the battery is charged, zinc is deposited on the negative electrode, and free bromine generated by the positive electrode is complexed by a bromine complexing agent; during discharging, the zinc deposited on the cathode is completely dissolved, the oily bromine complex in the electrolyte is converted into bromide ions again, and the electrolyte returns to the zinc bromide solution (ZnBr)2) And since the capacity of the battery during discharging is determined by the zinc loading on the surface of the electrode, the electrode does not participate in the reaction, so that the zinc-bromine liquid battery can realize 100% deep discharge theoretically, and the performance and the service life of the battery can not be influenced.
Compared with other iron-chromium flow batteries, zinc-nickel flow batteries, sodium polysulfide-bromine flow batteries and the like, the zinc-bromine flow battery has the advantages that ① is high in specific energy density, ② complex bromine is removed, electrolytes of the positive electrode and the negative electrode of the battery are completely consistent, cross contamination of the electrolytes is avoided, the theoretical life of the electrolytes is nearly unlimited, ③ the electrolytes are mainly composed of zinc bromide (oil field drilling completion fluid) and aqueous solutions, the safety coefficient of the system is high, dangerous accidents such as ignition and explosion are not prone to occurring, ④ zinc and bromine are common substances, the cost of the electrolytes is low, and the zinc-bromine flow battery has the advantage of being high in price.
The existing electrolyte formula of the zinc-bromine flow battery is mainly used for improving the energy efficiency of the battery from the aspects of reducing the self-discharge of the battery, inhibiting the hydrogen evolution reaction and increasing the conductivity of the battery, and the problems of short cycle life, low deep discharge efficiency and over-fast self-discharge of the battery generally exist. Meanwhile, the electrolyte related to the prior art is mainly suitable for a flow battery system with a circulating device, and the battery system is complex in structure, high in manufacturing cost and not beneficial to large-scale popularization and use.
Disclosure of Invention
In view of the above, the present invention is directed to provide an electrolyte for a static zinc-bromine liquid battery, so as to solve the problems of short cycle life, low deep discharge efficiency and fast self-discharge of the conventional zinc-bromine liquid battery.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
an electrolyte for a static zinc-bromine liquid battery mainly comprises zinc bromide, a bromine complexing agent, a dendrite inhibitor, a conductive agent, a pH regulator and distilled water.
Optionally, the electrolyte for the static zinc-bromine liquid battery has a pH value of 2.4-3.5.
Optionally, the molar concentration of the zinc bromide is 1.5-3.0 mol/L.
Optionally, the molar concentration of the bromine complexing agent is 0.015-0.03 mol/L.
Optionally, the volume concentration of the dendrite inhibitor is 3% to 10%.
Optionally, the molar concentration of the conductive agent is 0.05-1 mol/L.
Optionally, the bromine complexing agent is one or more of tetraethylammonium bromide, N-ethyl-N-methylmorpholine bromide, trimethylpropylammonium bromide, 1-ethyl-3-methylpyridine bromide, N-methyl-N-butylpyrrolidine bromide, 1-butyl-2, 3-dimethylpyridine bromide, 1-butyl-1-methylpyrrolidine bromide, N-methyl-N-ethylpyrrolidine bromide, tetraethylammonium bromide, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, tetraethylammonium chloride, N-ethyl-N-methylmorpholine chloride.
Optionally, the dendrite inhibitor is C1-14Monoalcohol, C1-10One or more of glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol dimethyl ether 1000 and polyethylene glycol dimethyl ether 2000.
Optionally, the conductive agent is one or more of perchlorate, nitrate, sulfate, halide, and halide hydrate.
Optionally, the pH regulator is one or more of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, citric acid, ammonia, sodium hydroxide, and potassium hydroxide.
Compared with the prior art, the electrolyte for the static zinc-bromine liquid battery has the following advantages:
according to the electrolyte for the static zinc-bromine liquid battery, the dendritic crystal inhibitor and the bromine complexing agent are added, and the pH value of the electrolyte is adjusted through the pH regulator, so that on one hand, the overgrowth of Zn crystal grains in the charging process can be effectively inhibited, the continuous and stable current in the charging and discharging process is kept, the energy efficiency and the cycle life of the battery are greatly improved under the condition of ensuring the reduction of the cost of the electrolyte, on the other hand, the self-discharging process of the zinc-bromine battery can be effectively inhibited, the manufacture of the static battery is realized, the cycle process of the electrolyte is avoided, when the electrolyte is used for a battery system, a cycle device can be removed, the structure of the liquid battery is simplified, and the difficulty and the cost of the manufacture process of the battery are greatly reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a charge-discharge efficiency curve of an electrolyte according to example 1 of the present invention;
FIG. 2 is a charge-discharge efficiency curve of the electrolyte of example 2 of the present invention;
FIG. 3 is a charge-discharge efficiency curve of the electrolyte of example 3 of the present invention;
FIG. 4 is a charge-discharge efficiency curve of the electrolyte of example 4 of the present invention;
FIG. 5 is a charge-discharge efficiency curve of the electrolyte of comparative example 1 of the present invention;
FIG. 6 is a charge-discharge efficiency curve of the electrolyte of comparative example 2 of the present invention;
FIG. 7 shows the surface morphology of charged Zn deposit in the electrolytes of example 4 and comparative example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail with reference to examples.
Example 1
An electrolyte for a static zinc-bromine liquid battery comprises the following basic components: zinc bromide (ZnBr)2) Tetraethylammonium bromide (TEA, bromine complexing agent), polyethylene glycol 400(PEG400, dendrite inhibitor), polyethylene glycol 200(PEG200, dendrite inhibitor), potassium chloride (conductive agent), ammonia water (pH regulator) and distilled water, wherein the molar concentration of zinc bromide is 2mol/L, the molar concentration of tetraethylammonium bromide is 0.015mol/L, the volume concentration of polyethylene glycol 400 is 4.5%, the volume concentration of polyethylene glycol 200 is 4.5%, and the molar concentration of potassium chloride is 0.05 mol/L.
The electrolyte for the static zinc-bromine liquid battery is prepared by the following method:
according to the formula, zinc bromide, tetraethyl ammonium bromide and potassium chloride are respectively dissolved in a proper amount of distilled water to prepare a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution;
uniformly mixing a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution, sequentially adding 1.5mL PEG400 and 1.5mL PEG200, uniformly stirring, adding distilled water to a constant volume of 30mL, and adjusting the pH value to 2.5 by using an appropriate amount of diluted ammonia water solution to obtain the electrolyte for the static zinc-bromine liquid battery.
Example 2
Electricity for static zinc-bromine liquid batteryThe electrolyte comprises the following basic components: zinc bromide (ZnBr)2) Tetraethylammonium bromide (TEA, bromine complexing agent), polyethylene glycol 400(PEG400, dendrite inhibitor), polyethylene glycol 200(PEG200, dendrite inhibitor), potassium chloride (conductive agent), ammonia water (pH regulator) and distilled water, wherein the molar concentration of zinc bromide is 2.5mol/L, the molar concentration of tetraethylammonium bromide is 0.03mol/L, the volume concentration of polyethylene glycol 400 is 3%, the volume concentration of polyethylene glycol 200 is 3%, and the molar concentration of potassium chloride is 0.05 mol/L.
The electrolyte for the static zinc-bromine liquid battery is prepared by the following method:
according to the formula, zinc bromide, tetraethyl ammonium bromide and potassium chloride are respectively dissolved in a proper amount of distilled water to prepare a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution;
uniformly mixing a zinc bromide aqueous solution, a tetraethylammonium bromide aqueous solution and a potassium chloride aqueous solution, sequentially adding 1mL PEG400 and 1mL PEG200, uniformly stirring, adding distilled water to a constant volume of 30mL, and adjusting the pH value to 2.5 by using an appropriate amount of diluted ammonia water solution to obtain the electrolyte for the static zinc-bromine liquid battery.
Example 3
An electrolyte for a static zinc-bromine liquid battery comprises the following basic components: zinc bromide (ZnBr)2) Tetraethylammonium bromide (TEA, bromine complexing agent), polyethylene glycol 400(PEG400, dendrite inhibitor), potassium chloride (conductive agent), ammonia water (pH regulator) and distilled water, wherein the molar concentration of zinc bromide is 2.5mol/L, the molar concentration of tetraethylammonium bromide is 0.015mol/L, the volume concentration of polyethylene glycol 400 is 6%, and the molar concentration of potassium chloride is 0.05 mol/L.
The electrolyte for the static zinc-bromine liquid battery is prepared by the following method:
according to the formula, zinc bromide, tetraethyl ammonium bromide and potassium chloride are respectively dissolved in a proper amount of distilled water to prepare a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution;
uniformly mixing a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution, adding 2mL PEG400, uniformly stirring, adding distilled water to a constant volume of 30mL, and adjusting the pH value to 3 by using an appropriate amount of diluted ammonia water solution to obtain the electrolyte for the static zinc-bromine liquid battery.
Example 4
An electrolyte for a static zinc-bromine liquid battery comprises the following basic components: zinc bromide (ZnBr)2) Tetraethylammonium bromide (TEA, bromine complexing agent), polyethylene glycol 400(PEG400, dendrite inhibitor), potassium chloride (conductive agent), ammonia water (pH regulator) and distilled water, wherein the molar concentration of zinc bromide is 3mol/L, the molar concentration of tetraethylammonium bromide is 0.015mol/L, the volume concentration of polyethylene glycol 400 is 6%, and the molar concentration of potassium chloride is 0.05 mol/L.
The electrolyte for the static zinc-bromine liquid battery is prepared by the following method:
according to the formula, zinc bromide, tetraethyl ammonium bromide and potassium chloride are respectively dissolved in a proper amount of distilled water to prepare a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution;
uniformly mixing a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution, adding 2mL PEG400, uniformly stirring, adding distilled water to a constant volume of 30mL, and adjusting the pH value to 3 by using an appropriate amount of diluted ammonia water solution to obtain the electrolyte for the static zinc-bromine liquid battery.
Comparative example 1
The electrolyte of this comparative example had the following basic components: 85g of zinc bromide, 95g of distilled water, 21g of potassium bromide, 20g of potassium chloride, 1.11g of acetic acid, 4.96g of 1-ethyl-2-methylpyridine bromide, 6.1g of tetraethylammonium bromide, 18-crown-60.55 g of tetraethylammonium bromide and 0.4g of hexadecyltrimethylammonium bromide.
According to the formula, the solid reagents are respectively dissolved in a proper amount of distilled water to prepare aqueous solutions of the solid reagents, the aqueous solutions are uniformly mixed, and the pH value is adjusted to 3.0-3.5 by acetic acid, so that the electrolyte of the zinc-bromine liquid battery in the comparative example is obtained.
Comparative example 2
The electrolyte of this comparative example contains the following basic components: zinc bromide (ZnBr)2) Tetraethylammonium bromide (TEA,bromine complexing agent), polyethylene glycol 400(PEG400, dendrite inhibitor), potassium chloride (conductive agent), ammonia water (pH regulator) and distilled water, wherein the molar concentration of zinc bromide is 1.5mol/L, the volume concentration of polyethylene glycol 400 is 3%, and the molar concentration of potassium chloride is 0.05 mol/L.
The electrolyte for the static zinc-bromine liquid battery is prepared by the following method:
according to the formula, zinc bromide, tetraethyl ammonium bromide and potassium chloride are respectively dissolved in a proper amount of distilled water to prepare a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution;
uniformly mixing a zinc bromide aqueous solution, a tetraethyl ammonium bromide aqueous solution and a potassium chloride aqueous solution, adding 1mL of polyethylene glycol 400, uniformly stirring, adding distilled water to a constant volume of 30mL, and adjusting the pH value to 2.5 by using a proper amount of diluted ammonia water solution to obtain the electrolyte for the static zinc-bromine liquid battery.
The electrolytes of examples 1 to 4 and comparative examples 1 to 2 of the present invention were injected into a device for rapidly testing the efficiency of a liquid battery to prepare a single cell, the battery and a test instrument were connected by a wire, and the test parameters were set as follows: charging current is 0.08A, charging voltage is 2V, and charging is carried out for 5 min; the discharge current is 0.15A, and the discharge cut-off voltage is 0.1V; the number of charge and discharge cycles was 100.
According to the battery charge and discharge data recorded by the testing equipment, the charge and discharge efficiency curves of the electrolytes of examples 1 to 4 are calculated and are respectively shown in fig. 1, fig. 2, fig. 3 and fig. 4, the charge and discharge efficiency curves of the electrolytes of comparative examples 1 to 2 are shown in fig. 5 and fig. 6, the surface morphologies of the charged deposited Zn of the electrolytes of example 4 and comparative example 1 are shown in fig. 7, and the average charge and discharge efficiency of the electrolytes of examples 1 to 4 and comparative examples 1 to 2 is shown in table 1.
As can be seen from Table 1, the charge-discharge efficiency of the single cell manufactured by using the electrolyte of examples 1-4 of the invention is more than 93%, which is higher than that of comparative examples 1-2. As can be seen from fig. 1 to 6, the electrolytes of examples 1 to 4 of the present invention can maintain the continuous stability of the cycle efficiency during 100 charges and discharges, relative to the electrolytes of comparative examples 1 to 2.
As can be seen from fig. 7, the electrolyte of example 4 of the present invention can better inhibit the growth of Zn during the charging process (fig. 7a), and the electrolyte of comparative example 1 has coarse Zn grains (fig. 7b), so that the present invention has higher charging and discharging efficiency than the comparative example.
TABLE 1
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The electrolyte for the static zinc-bromine liquid battery is characterized by mainly comprising zinc bromide, a bromine complexing agent, a dendrite inhibitor, a conductive agent, a pH regulator and distilled water.
2. The electrolyte for a static zinc-bromine liquid battery as claimed in claim 1, wherein the pH value of the electrolyte for a static zinc-bromine liquid battery is 2.4-3.5.
3. The electrolyte for the static zinc-bromine liquid battery as claimed in claim 1, wherein the molar concentration of the zinc bromide is 1.5-3.0 mol/L.
4. The electrolyte for the static zinc-bromine liquid battery as claimed in claim 1, wherein the molar concentration of the bromine complexing agent is 0.015-0.03 mol/L.
5. The electrolyte for a static zinc-bromine liquid battery according to claim 1 wherein the volume concentration of the dendrite inhibitor is 3% to 10%.
6. The electrolyte for the static zinc-bromine liquid battery as claimed in claim 1, wherein the molar concentration of the conductive agent is 0.05-1 mol/L.
7. The electrolyte for a static zinc-bromine liquid battery according to claim 1 or 4, the bromine complexing agent is one or more of tetraethylammonium bromide, N-ethyl-N-methylmorpholine bromide, trimethylpropylammonium bromide, 1-ethyl-3-methylpyridine bromide, N-methyl-N-butylpyrrolidine bromide, 1-butyl-2, 3-dimethylpyridine bromide, 1-butyl-1-methylpyridine bromide, N-methyl-N-ethylpyrrolidine bromide, tetraethylammonium bromide, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, tetraethylammonium chloride and N-ethyl-N-methylmorpholine chloride.
8. The electrolyte for a static zinc-bromine liquid battery according to claim 1 or 5 characterized in that the dendrite inhibitor is C1-14Monoalcohol, C1-10One or more of glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol dimethyl ether 1000 and polyethylene glycol dimethyl ether 2000.
9. The electrolyte for a static zinc-bromine liquid battery according to claim 1 or 6, characterized in that the conductive agent is one or more of perchlorate, nitrate, sulfate, halide hydrate.
10. The electrolyte for a static zinc-bromine liquid battery according to claim 1, wherein the pH regulator is one of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, citric acid, ammonia water, sodium hydroxide and potassium hydroxide.
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| CN114497660A (en) * | 2020-11-12 | 2022-05-13 | 中国科学院大连化学物理研究所 | Application of complexing agent in zinc-bromine storage battery electrolyte |
| CN114614038A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Zinc-bromine flow battery electrolyte and application thereof in zinc-bromine flow battery |
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| WO2024097835A1 (en) * | 2022-11-03 | 2024-05-10 | EOS Energy Technology Holdings, LLC | Mixed polyhalide electrolytes for a static battery and a method for fabricating a static battery cell |
| GB2625929A (en) * | 2023-11-22 | 2024-07-03 | Offgrid Energy Labs Private Ltd | Electrolyte for ultra-efficient and temperature-resilient static zinc-based battery |
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