CN118016948A - Multi-active-substance electrolyte and flow battery comprising same - Google Patents
Multi-active-substance electrolyte and flow battery comprising same Download PDFInfo
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- CN118016948A CN118016948A CN202410288398.7A CN202410288398A CN118016948A CN 118016948 A CN118016948 A CN 118016948A CN 202410288398 A CN202410288398 A CN 202410288398A CN 118016948 A CN118016948 A CN 118016948A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 183
- 239000013543 active substance Substances 0.000 title claims abstract description 54
- 239000011149 active material Substances 0.000 claims abstract description 116
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 239000011135 tin Substances 0.000 claims abstract description 4
- -1 vanadyl bromide Chemical compound 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 22
- 239000003115 supporting electrolyte Substances 0.000 claims description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 6
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-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
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 125000005287 vanadyl group Chemical group 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 18
- 238000004146 energy storage Methods 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229940006460 bromide ion Drugs 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000006479 redox reaction Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 230000032895 transmembrane transport 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
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
Landscapes
- 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)
- Fuel Cell (AREA)
Abstract
The invention provides a multi-active-substance electrolyte and a flow battery comprising the same, and belongs to the technical field of flow batteries. The multi-active substance electrolyte comprises a first active substance and a second active substance which can respectively participate in electrochemical energy storage, wherein the first active substance comprises vanadium ions; wherein, in the case that the electrolyte is a positive electrode electrolyte, the element of the second active material includes at least one of iron, titanium, manganese, chromium, copper, cerium, iodine, or bromine; in the case where the electrolyte is a negative electrode electrolyte, the element of the second active material includes at least one of iron, tin, chromium, copper, or sulfur. By adding various active substances capable of respectively participating in electrochemical energy storage into the electrolyte of the flow battery, the energy density of the all-vanadium flow battery is improved, and the operating temperature threshold and the power density of the all-vanadium flow battery are improved.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a multi-active-substance electrolyte and a flow battery comprising the same.
Background
The development and utilization of renewable energy sources are important measures for solving the problems of energy shortage and environmental pollution. Renewable energy sources represented by wind energy and solar energy are greatly developed, but the renewable energy sources often have the characteristics of intermittence, volatility, strong time variability and the like, the direct grid connection of the generated electricity can cause great impact on the safe and stable operation of the power grid. To solve this problem, developing a high-efficiency, stable, low-cost large-scale electricity storage system becomes an effective approach. In the related electricity storage technology, the flow battery has the advantages of independent capacity and power, good expandability, high safety, long cycle life, short response time and the like, and is widely focused in the field of large-scale energy storage.
The vanadium redox flow battery is a mature redox flow battery system, commercialization to a certain extent has been realized, wherein the electrolyte is used as a carrier of active substances, is one of important components in the vanadium redox flow battery, is limited by the concentration and performance of the electrolyte, has the problems of low energy density and narrow working temperature threshold, and makes the vanadium redox flow battery difficult to further develop. Furthermore, in many flow battery systems and technologies, the high energy density characteristics are often difficult to combine with the high power density characteristics, both of which are difficult to combine.
Disclosure of Invention
In view of the above problems, a primary object of the present invention is to provide a multi-active material electrolyte and a flow battery including the same. By adding various active substances capable of respectively participating in electrochemical energy storage into the electrolyte of the flow battery, the energy density of the all-vanadium flow battery is improved, and the operating temperature threshold and the power density of the all-vanadium flow battery are improved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
In a first aspect, the present invention provides a multi-active material electrolyte comprising a first active material and a second active material capable of participating in electrochemical energy storage, respectively, the first active material comprising vanadium ions; wherein, in the case that the multi-active material electrolyte is a positive electrode electrolyte, the element of the second active material includes at least one of iron, titanium, manganese, chromium, copper, cerium, iodine, or bromine; in the case where the multi-active material electrolyte is a negative electrode electrolyte, the element of the second active material includes at least one of iron, tin, chromium, copper, or sulfur.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes at least one of ferrous ions and bromide ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the second active material includes ferric ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes ferrous ions and bromide ions.
According to an embodiment of the present invention, the concentration of the first active material is 0.1 to 2.2mol/L, and the concentration of the second active material is 0.1 to 15.0mol/L.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the first active material includes at least one of trivalent vanadium ions, tetravalent vanadium ions, or pentavalent vanadium ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the first active material includes at least one of divalent vanadium ions, trivalent vanadium ions, or tetravalent vanadium ions.
According to an embodiment of the present invention, the first active material is at least one selected from vanadyl sulfate, vanadyl pentoxide, vanadyl bromide, and vanadyl chloride as a vanadium source.
According to an embodiment of the present invention, the multi-active material electrolyte further includes a supporting electrolyte including at least one of hydrochloric acid, sulfuric acid, hypochlorous acid, perchloric acid, sodium chloride, potassium chloride, and ammonium chloride.
According to an embodiment of the present invention, the supporting electrolyte includes at least one of hydrochloric acid and sulfuric acid.
According to an embodiment of the present invention, the supporting electrolyte includes hydrochloric acid and sulfuric acid.
According to an embodiment of the present invention, the above supporting electrolyte provides a total hydrogen ion concentration of 0.01 to 10mol/L.
In another aspect, the invention provides a flow battery comprising the multi-active electrolyte described above.
According to the embodiment of the invention, by utilizing the characteristic that a plurality of active substances can coexist in the same system, a plurality of active substances which can respectively participate in electrochemical energy storage are added into the electrolyte, and the volumetric energy density of the flow battery is effectively improved by improving the total concentration of the active substances and the number of electrons transferred per unit volume of the electrolyte, and the flow battery has higher power density; by the mutual complexation between ions, the temperature window in which the battery operates and the solubility properties of the respective active materials can be enlarged.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of embodiments of the present invention with reference to the accompanying drawings, in which:
fig. 1 is a graph showing the relationship between the specific capacity of charge and discharge volume and voltage of a flow battery according to embodiment 1 of the present invention;
fig. 2 is a graph of the relationship between the specific capacity of charge and discharge volume and voltage of the flow battery provided in example 2 of the present invention;
FIG. 3 is a graph showing the relationship between the specific capacity of charge and discharge volume and voltage of the flow battery provided in example 3 of the present invention;
FIG. 4 is a graph showing the relationship between charge-discharge energy density and voltage of the flow battery according to example 3 of the present invention;
fig. 5 is a graph of the relationship between the specific capacity of charge and discharge volume and voltage of the flow battery provided in example 4 of the present invention;
Fig. 6 is a graph of the relationship between the specific capacity of charge and discharge volume and voltage of the flow battery provided in example 5 of the present invention;
FIG. 7 is a graph showing the relationship between charge-discharge energy density and voltage of the flow battery provided in comparative example 1 of the present invention;
FIG. 8 is a graph showing the relationship between charge-discharge energy density and voltage of the flow battery provided in comparative example 2 of the present invention;
FIG. 9 is a photograph of a low temperature performance test of test example 1; and
FIG. 10 is a photograph of a high temperature performance test of test example 2.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The electrolyte is limited by the concentration and the performance of the electrolyte in the all-vanadium redox flow battery, and the problems of low energy density and narrow working temperature threshold value make the all-vanadium redox flow battery difficult to further develop.
In the related art, the concentration of active substances in the electrolyte and the working temperature threshold value are mainly improved by the following methods: firstly, a plurality of supporting electrolyte mixed systems are used, so that the solubility of vanadium ions is increased as much as possible, but the increased solubility of the method is limited, and the influence on the working temperature threshold value is small; secondly, a high-performance electrolyte additive is developed, but the additive has the risk of increasing polarization and side reaction, so that the problem of insufficient solubility of active substances is difficult to thoroughly solve fundamentally, and the energy density and the active substance utilization rate of the all-vanadium redox flow battery are difficult to further improve by the development and the use of the additive.
In addition, generally in a high energy density flow battery, higher concentration of active material and lower operating current density are meant, while in a high power density flow battery, limited solubility of active material is meant to limit further increases in the energy density of the battery. The energy density is used for representing the energy stored in the battery of unit weight or volume, and the power density is used for representing the energy output rate of the battery of unit weight or volume when discharging. In many flow battery systems and technologies, the high energy density characteristics are often difficult to combine with the high power density characteristics, both of which are difficult to combine.
In the process of realizing the invention, unlike the fixed thought of energy storage of a single active substance, the invention is innovatively designed aiming at the defect of electrolyte of the single active substance. By adding various active substances capable of respectively participating in electrochemical energy storage into the electrolyte of the flow battery, the energy density of the all-vanadium flow battery is improved, and the operating temperature threshold and the power density of the all-vanadium flow battery are improved.
Specifically, according to an embodiment of the present invention, there is provided a multi-active material electrolyte including a first active material and a second active material capable of participating in electrochemical energy storage, respectively, the first active material including vanadium ions; wherein, in the case that the multi-active material electrolyte is a positive electrode electrolyte, the element of the second active material includes at least one of iron, titanium, manganese, chromium, copper, cerium, iodine, or bromine; in the case where the multi-active material electrolyte is a negative electrode electrolyte, the element of the second active material includes at least one of iron, tin, chromium, copper, or sulfur.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes at least one of iron ions, titanium ions, manganese ions, chromium ions, copper ions, cerium ions, iodine simple substance, bromine ions, or bromine simple substance.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the second active material includes at least one of iron ions, tin simple substances, chromium ions, chromium simple substances, copper ions, copper simple substances, or polysulfide ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes at least one of ferrous ions, titanium ions, manganese ions, chromium ions, copper ions, cerium ions, iodine ions, or bromine ions when the electrolyte is not charged.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the second active material includes at least one of ferric ion, stannous ion, trivalent chromium ion, monovalent copper ion, or polysulfide ion when the electrolyte is not charged.
According to an embodiment of the present invention, the products of the active material pair before and after the valence change before and after the charge and discharge include, but are not limited to, physical states such as ionic state, solid state, liquid state, gas state, plasma state, and the like.
According to the embodiment of the invention, various active substances existing in the electrolyte can perform high-reversibility electrochemical oxidation-reduction reaction, participate in electric energy storage and release, do not generate mutual chemical reaction in the process of converting electric energy into chemical energy, do not generate mutual interference in the electrochemical reaction of the various active substances, can perform graded energy storage according to different potentials, and can perform oxidation-reduction reaction between active substances with similar or same potentials.
According to the embodiment of the present invention, various active materials can be stably present in an electrolyte for a long period of time.
According to the embodiment of the invention, in the electric energy storage process, according to the theoretical capacity of the tetravalent vanadium ion concentration contained in the electrolyte, all the vanadium ions at the negative electrode side can be charged to the trivalent vanadium ion state through stepped constant current charging, and the reaction between the trivalent vanadium ions at the negative electrode side and the divalent vanadium ions at the negative electrode side is used as the first energy storage reaction at the negative electrode side. Meanwhile, the reaction between tetravalent vanadium ions and pentavalent vanadium ions on the positive electrode side is used as the first energy storage reaction on the positive electrode side.
Wherein, the energy storage electrochemical reaction in the electrolyte is as follows:
negative electrode side:
Positive electrode side:
Wherein X and Y are respectively second active substances except vanadium ions at the negative electrode side and the positive electrode side, and at least one kind of active substances exists in the electrolyte X, Y, so that the number of transferred electrons in unit volume of the electrolyte is increased; n and m are positive integers.
According to the embodiment of the invention, by utilizing the characteristic that a plurality of active substances can coexist in the same system, a plurality of active substances which can respectively participate in electrochemical energy storage are added into the electrolyte, and the volumetric energy density of the flow battery is effectively improved by improving the total concentration of the active substances and the number of electrons transferred per unit volume of the electrolyte, and the flow battery has higher power density; by the mutual complexation between ions, the temperature window in which the battery operates and the solubility properties of the respective active materials can be enlarged.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes at least one of ferrous ions and bromide ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the second active material includes ferrous ions.
According to the embodiment of the invention, the electrolyte is assembled into the flow battery energy storage system for practical application, and various active substances contained in the electrolyte can be subjected to graded oxidation-reduction reaction or simultaneous oxidation-reduction reaction. For example, the vanadium ions and the bromide ions having similar potentials can react simultaneously by the interaction between the ions, and in this case, Y in the formula (4) represents the bromide ion. The potential difference between the iron ions and the vanadium ions is large, and no strong interaction exists, so that a step-type fractional energy storage process can be performed, and at the moment, X and Y in the formula (2) and the formula (4) can both represent the iron ions.
According to the embodiment of the invention, the interaction between the bromide ion and the metal ion can improve the thermal stability of the metal ion in the aqueous solution, wherein the hydrolytic precipitation of the metal ion is restrained at high temperature, and the freezing point of the electrolyte is lowered at low temperature.
According to the embodiment of the invention, various active substances perform an energy storage process according to the characteristics of the active substances, participate in oxidation-reduction reaction, and the characteristics of energy storage by the various active substances are utilized on the basis of keeping the original power characteristics so as to improve the energy density of the electrolyte in unit volume. The active substances can participate in the reaction at the same time, and can also carry out grading energy storage according to different potentials.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes ferrous ions and bromide ions.
According to the embodiment of the invention, under the condition that the electrolyte simultaneously comprises the iron ions and the bromine ions, through the mutual complexation between the iron ions and the bromine ions and between the iron ions and the vanadium ions, the temperature window of battery operation and the dissolution performance of each active substance can be enlarged, the total concentration of the active substances and the number of transferred electrons in unit volume of the electrolyte are further improved, so that the volumetric energy density of the flow battery is effectively improved, and the flow battery has higher power density.
According to an embodiment of the present invention, the concentration of the first active material is 0.1 to 2.2mol/L, preferably 0.5 to 2.0mol/L, and more preferably 1.0 to 1.8mol/L.
According to an embodiment of the present invention, the concentration of the first active material may be 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1.0mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L and 2.2mol/L, preferably 1.5mol/L.
According to an embodiment of the present invention, the concentration of the second active material is 0.1 to 15.0mol/L, preferably 1 to 12mol/L, more preferably 1 to 8mol/L, and even more preferably 1 to 5mol/L.
According to an embodiment of the present invention, the concentration of the second active material may be 0.1mol/L、0.5mol/L、1.0mol/L、2.0mol/L、1.0mol/L、1.5mol/L、3.0mol/L、5.0mol/L、7.0mol/L、10.0mol/L、12.0mol/L、15.0mol/L,, preferably 3mol/L.
According to an embodiment of the present invention, the concentration of the first active material and the concentration of the second active material are too high, which will reduce the power density of the battery; too low a concentration of the first active material and a concentration of the second active material will reduce the volumetric energy density of the battery.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a positive electrode electrolyte, the first active material includes at least one of trivalent vanadium ions, tetravalent vanadium ions, or pentavalent vanadium ions.
According to an embodiment of the present invention, in the case where the multi-active material electrolyte is a negative electrode electrolyte, the first active material includes at least one of divalent vanadium ions, trivalent vanadium ions, or tetravalent vanadium ions.
According to an embodiment of the present invention, in the case where the above multi-active material electrolyte is a positive electrode electrolyte, vanadium ions may exist in a tetravalent form as the first active material when not charged.
According to an embodiment of the present invention, in the case where the above multi-active material electrolyte is a negative electrode electrolyte, vanadium ions may exist in trivalent form as the first active material when not charged.
According to an embodiment of the present invention, the first active material is at least one selected from vanadyl sulfate, vanadyl pentoxide, vanadyl bromide, and vanadyl chloride as a vanadium source, and preferably vanadyl sulfate.
According to an embodiment of the present invention, the multi-active material electrolyte further includes a supporting electrolyte including at least one of hydrochloric acid, sulfuric acid, hypochlorous acid, perchloric acid, sodium chloride, potassium chloride, and ammonium chloride.
According to an embodiment of the present invention, the supporting electrolyte includes at least one of hydrochloric acid and sulfuric acid.
According to an embodiment of the present invention, the supporting electrolyte is used to provide transmembrane carriers, form an internal pathway of the cell and reduce transmembrane transport polarization, and the active material and the supporting electrolyte do not react with each other.
According to the embodiment of the invention, the total ion concentration of the active substances in the positive and negative electrode electrolyte and the supporting electrolyte should be similar, so that serious water migration phenomenon between the positive and negative electrodes caused by excessive concentration difference or viscosity difference is avoided.
According to the embodiment of the invention, the active substance and the supporting electrolyte have strong ionization effect in the solvent, so that a multielement high-entropy ion system can be formed, the solubility of the active substance under the liquid state condition is increased, the stability and the cycle life of the active substance in the working process are improved, the number of carriers in the electrolyte can be increased, and the internal polarization of a battery is reduced; the ion generated by ionization of the supporting electrolyte is used as an active substance, and the extremely high solubility of the ion can greatly increase the energy density of the flow battery; by utilizing the interaction between ion active substances, the working temperature threshold of the flow battery can be improved, so that the low temperature resistance and the high temperature resistance of the flow battery are improved simultaneously.
According to an embodiment of the present invention, the supporting electrolyte includes hydrochloric acid.
According to the embodiment of the invention, the interaction between the chloride ions and the metal ions can improve the thermal stability of the metal ions in the aqueous solution, wherein the hydrolytic precipitation of the metal ions is inhibited at high temperature, and the freezing point of the electrolyte is lowered at low temperature.
According to an embodiment of the present invention, the supporting electrolyte includes hydrochloric acid and sulfuric acid.
According to the embodiment of the invention, the solubility of the active substance in the solution can be improved by utilizing the polyion effect of hydrochloric acid and sulfuric acid.
According to an embodiment of the present invention, in the case where the above-described multi-active material electrolyte is a positive electrode electrolyte, the second active material includes bromide ions, and the supporting electrolyte includes hydrochloric acid and sulfuric acid.
According to the embodiment of the invention, under the mixed acid system containing chloride ions, the chloride ions can be complexed with bromine simple substances in the solution, the oxidation-reduction potential of the chloride ions is higher, the reaction is less likely to occur, and the utilization rate of active substances in the electrolyte can be further improved.
According to an embodiment of the present invention, the above supporting electrolyte provides a total hydrogen ion concentration of 0.01 to 10mol/L.
According to the embodiment of the invention, the solubility of the active substances in the solvent can be improved by reasonable design of the solvent, a liquid environment with high flow characteristics is provided for the electrolyte, the energy density is increased, the flow resistance is reduced, and the system energy efficiency of the energy storage system is improved.
According to an embodiment of the present invention, the solvent may be water.
In another aspect, the invention provides a flow battery comprising the multi-active electrolyte described above.
According to an embodiment of the present invention, the battery further includes an ion separator, and the positive electrode electrolyte and the negative electrode electrolyte are respectively disposed on two sides of the ion separator, and are selected from any one of a perfluorosulfonic acid membrane, a porous polyolefin membrane, a sulfonated polyether ether ketone membrane, and a polybenzimidazole membrane, preferably a perfluorosulfonic acid membrane.
According to the embodiment of the invention, when the electrolyte is used for assembling the flow battery and storing energy in practical application, the electrolyte has a remarkable effect in improving the energy density. For example, when bromide ion is used as the second active material, the flow battery has excellent rate performance, higher working temperature threshold and energy density which is more than 1.5 times that of the traditional all-vanadium electrolyte, and can work in a wider temperature range without generating precipitation or crystallization.
According to the embodiment of the invention, the energy density of the flow battery prepared from the multi-active substance electrolyte in actual operation reaches 17.5-23 Wh/L.
According to an embodiment of the present invention, when the second active material is a bromide ion, the positive electrode electrolyte may be prepared by: and (3) putting the weighed vanadyl sulfate solid into a beaker, measuring the required concentrated sulfuric acid and concentrated hydrobromic acid according to the calculated mass concentration of the substances, adding the concentrated sulfuric acid and the concentrated hydrobromic acid into the vanadyl sulfate solid, stirring, slowly adding a proper amount of deionized water into the beaker in the process, and then magnetically stirring for not less than 2 hours. And transferring the electrolyte into a volumetric flask for constant volume operation until no solid remains in the beaker.
According to an embodiment of the present invention, when the second active material is bromide, the negative electrode electrolyte may be prepared by: dividing the prepared positive electrode electrolyte into two parts with equal volume, respectively placing the two parts into a liquid storage tank of a positive electrode and a negative electrode, assembling a battery, introducing nitrogen into the liquid storage tank for more than one minute, and then tightly covering a liquid storage tank cover to carry out electrolysis. Constant current electrolysis is performed by using an electrochemical method, and stepped current is applied to the constant current electrolysis by a charge-discharge tester for electrolysis. Charging to a cut-off voltage of 1.6V at a current density of 400mA/cm 2、300mA/cm2、200mA/cm2、100mA/cm2、50mA/cm2, and stopping the electrolysis process after the total charging capacity reaches the theoretical capacity value of the electrolyte at the negative electrode side and the vanadium ions in the electrolyte at the negative electrode side are completely electrolyzed to trivalent vanadium ions.
The following describes the technical scheme of the invention in detail by listing a plurality of specific embodiments. It should be noted that the following specific embodiments are only examples and are not intended to limit the present invention.
Example 1
In this embodiment, a negative electrode electrolyte and a positive electrode electrolyte having a plurality of active materials are applied to a flow battery. Wherein the negative electrode side electrolyte contains 20ml of 1.5M trivalent vanadium ions, 1.5M trivalent iron ions, 1.5M sulfate ions, 3.8M hydrogen ions and 5.3M chloride ions; the positive electrode side electrolyte contained 20ml of tetravalent vanadium ions of 1.5M, divalent iron ions of 1.5M, sulfate ions of 1.5M, hydrogen ions of 3.8M and chloride ions of 5.3M. The porous graphite felt is used as an electrode, the proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 3mm is compressed to be 2mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this example was subjected to charge and discharge tests under constant current density conditions with 1.7V and 0.5V as charge cut-off conditions and discharge cut-off conditions, respectively, and the test chart is shown in fig. 1. The charge-discharge curve shows two obvious platforms because the iron ions and the vanadium ions exist in the positive and negative electrolyte as active substances at the same time, and compared with an electrolyte system with single active substances, the electrolyte with multiple active substances in which the vanadium ions exist at the same time has the advantages that the high power density is reserved under the system of all metal ions, and the energy density is improved. The theoretical energy density can reach 28.81Wh/L, the maximum energy density in actual operation is 19.3Wh/L, the electrolyte utilization rate is 77.1%, and the operation can be performed under the current density of 300mA cm -2.
Example 2
In this embodiment, a positive electrode electrolyte having a plurality of active materials is applied to a flow battery. Wherein the negative electrode side electrolyte contains 1.5M trivalent vanadium ions, 1.5M sulfate ions, 3M hydrogen ions and 3M chloride ions, and the volume of the negative electrode electrolyte is 40ml; the positive electrode side electrolyte contained 1.5M tetravalent vanadium ions, 1.5M divalent iron ions, 1.5M sulfate ions, 3M hydrogen ions and 4.5M chloride ions, and the positive electrode electrolyte volume was 20ml. The porous graphite felt is used as an electrode, the proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 1.7mm is compressed to the thickness of 1mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this example was subjected to charge and discharge tests under constant current density conditions with 1.7V and 0.5V as charge cut-off conditions and discharge cut-off conditions, respectively, and the test chart is shown in fig. 2. Wherein, because the iron ions and the vanadium ions exist in the positive electrode electrolyte as active substances at the same time, the charge-discharge curve presents two obvious energy storage platforms, and the energy density of the system is further improved. The theoretical energy density is 28.81Wh/L, and the actual operating energy density can reach 23Wh/L.
Example 3
In this embodiment, a positive electrode electrolyte having a plurality of active materials is applied to a flow battery. Wherein the negative electrode side electrolyte contains 1.5M trivalent vanadium ions, 1.5M sulfate ions, 3M hydrogen ions and 3M bromide ions, and the volume of the negative electrode electrolyte is 40ml; the positive electrode side electrolyte contained 1.5M tetravalent vanadium ions, 1.5M sulfate ions, 3M hydrogen ions and 3M bromide ions, and the volume of the positive electrode electrolyte was 20ml. The porous graphite felt is used as an electrode, the proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 3mm is compressed to be 2mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this example was subjected to charge and discharge tests under constant current density conditions, with 2.0V and 0.6V as charge cut-off conditions and discharge cut-off conditions, respectively, as shown in fig. 3 and 4, wherein the current density of fig. 4 was 200mA cm -2. As the bromide ion and the vanadium ion are simultaneously used as active substances to be present in the positive electrode electrolyte and the potentials of the bromide ion and the vanadium ion are similar, when the vanadium and the bromine are simultaneously subjected to oxidation-reduction reaction, two obvious charge-discharge platforms do not appear, but the energy density of the system is further improved compared with that of the electrolyte with a single active substance, and the power density performance is maintained. The energy density in the system can reach 40.2Wh/L theoretically, the energy density in actual operation reaches 22.77Wh/L, and the system can operate at the current density of 400mA cm -2.
Example 4
In this embodiment, a positive electrode electrolyte having a plurality of active materials is applied to a flow battery. Wherein the negative electrode side electrolyte contains 1.5M trivalent vanadium ions, 1.5M sulfate ions, 7.2M hydrogen ions, 3M bromine ions and 4.2M chloride ions, and the volume of the negative electrode electrolyte is 40ml; the positive electrode side electrolyte contained 1.5M tetravalent vanadium ions, 1.5M sulfate ions, 7.2M hydrogen ions, 3M bromide ions and 4.2M chloride ions, and the positive electrode electrolyte volume was 20ml. The porous graphite felt is used as an electrode, the proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 1.7mm is compressed to be 0.5mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this example was subjected to charge and discharge tests under constant current density conditions with 2.0V and 0.6V as charge cut-off conditions and discharge cut-off conditions, respectively, and a test chart is shown in fig. 5. Compared with example 3, the mixed acid system of sulfuric acid and hydrochloric acid is adopted as the supporting electrolyte in example 4, and the utilization rate of bromide ions is higher under the mixed acid system containing chloride ions, so that the utilization rate of the electrolyte is improved. The energy efficiency of the operation under 400mA cm -2 is greatly improved. The theoretical energy density can reach 20.1Wh/L, the energy density of actual operation can reach 17.5Wh/L, and the utilization rate of electrolyte can reach 87%.
Example 5
In this embodiment, a positive electrode electrolyte and a negative electrode electrolyte having a plurality of active materials are applied to a flow battery. Wherein the negative electrode side electrolyte contains 1.0M trivalent vanadium ions, 1.0M trivalent iron ions, 6.0M hydrogen ions, 3.0M chloride ions and 4.0M sulfate ions, and the volume of the negative electrode electrolyte is 20ml; the positive electrode side electrolyte contained 1.0M tetravalent vanadium ion, 1.0M sulfate ion, 7.2M hydrogen ion, 7.2M bromide ion, and the positive electrode electrolyte volume was 20ml. The porous graphite felt is used as an electrode, the N212 proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 4.6mm is compressed to be 2mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this example was subjected to a charge and discharge test under a constant current density of 100mA/cm 2 with 1.6V and 0.2V as a charge cut-off condition and a discharge cut-off condition, respectively, and a test chart is shown in FIG. 6. In this example, positive and negative electrode sides each contain an active material, and the positive electrode side uses tetravalent vanadium ions and bromide ions as active materials, and the negative electrode side uses trivalent vanadium ions and trivalent iron ions as active materials. The battery can be charged and discharged normally, the theoretical energy density is 21.04Wh/L, and the actual running energy density is 10.73Wh/L. The inventors analyzed the reasons why the above-described battery performance was not very desirable, and considered possible reasons to include: the oxidation-reduction potential of the iron ions on the negative electrode side is higher, the potential difference between the iron ions and the active material on the positive electrode side is too small, the discharge depth of the battery is insufficient, the utilization rate of the electrolyte is lower, and the energy density is improved less.
The electrochemical reaction of energy storage in the electrolyte is as follows:
Positive electrode side:
negative electrode side:
Comparative example 1
In this comparative example, an all-vanadium electrolyte was applied to a flow battery. Wherein the positive and negative electrodes are respectively 20ml of electrolyte, and when not charged, the positive electrode electrolyte is 1.5M tetravalent vanadium ion, 3M hydrogen ion and 3M sulfate ion, and the negative electrode is 1.5M trivalent vanadium ion, 3M hydrogen ion and 3M sulfate ion. The maximum energy density of discharge is 12.32Wh/L. The porous graphite felt is used as an electrode, the proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 3mm is compressed to be 2mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this comparative example was subjected to charge and discharge tests under constant current density conditions, and the charge and discharge tests were performed under conditions of a current density of 200mA cm -2 with 1.7V and 0.5V as charge cut-off conditions and discharge cut-off conditions, respectively, as shown in FIG. 7. The maximum energy density of discharge is 12.32Wh/L.
Comparative example 2
In this comparative example, an all-vanadium electrolyte was applied to a flow battery. Wherein the negative electrode side electrolyte contains 1.0M trivalent vanadium ions, 6.0M hydrogen ions and 4.0M sulfate ions, and the volume of the negative electrode electrolyte is 20ml; the positive electrode side electrolyte contained 1.0M tetravalent vanadium ions, 6.0M hydrogen ions, 4.0M sulfate ions, and the positive electrode electrolyte volume was 20ml. The porous graphite felt is used as an electrode, the N212 proton exchange membrane is used as an ion diaphragm, the electrode with the thickness of 4.6mm is compressed to be 2mm, and the projection area of the electrode is 4cm 2.
The flow battery prepared in this comparative example was subjected to a charge-discharge test under a constant current density of 100mA/cm 2 with 1.6V and 0.2V as a charge cut-off condition and a discharge cut-off condition, respectively, and a test chart is shown in FIG. 8. Its theoretical energy density is 16.88Wh/L, and its actual running energy density is 9.61Wh/L
Test example 1
In this test example, electrolytes having various active materials were subjected to low-temperature experimental comparison.
Wherein the first row of electrolyte contains 1.5M trivalent vanadium ions, 4.5M sulfate ions and 6M hydrogen ions; the second row of electrolyte contains 1.5M trivalent vanadium ions, 1.5M sulfate ions, 6M hydrogen ions and 6M bromide ions.
The two electrolytes are simultaneously put into-25 ℃ for low-temperature preservation, and recorded every 8 hours, and the test result is shown in figure 9. As can be seen from fig. 9, the all-vanadium electrolyte containing a single active material rapidly exhibits crystallization and icing in a low temperature environment of-25 c or less, whereas the electrolyte containing a plurality of active materials has good liquid conditions in a low temperature environment, and thus has more excellent low temperature resistance.
Test example 2
In this test example, electrolytes having various active materials were subjected to high-temperature experimental comparison.
Wherein the first row of electrolyte contains 1.5M pentavalent vanadium ions, 4.5M sulfate ions and 6M hydrogen ions; the second row of electrolyte contains 1.5M of pentavalent vanadium ions, 1.5M of sulfate ions, 6M of hydrogen ions, 3M of bromine ions and 1.5M of bromine simple substances.
The two electrolytes are simultaneously put into 60 ℃ for high-temperature preservation, and recorded every 8 hours, and the test results are shown in figure 10. As can be seen from fig. 10, the all-vanadium electrolyte containing a single active material rapidly shows precipitation of pentavalent vanadium ions in a high temperature environment of 60 ℃ or more, and the precipitation belongs to an irreversible side reaction, while the electrolyte containing a plurality of active materials does not show any solid matters in a high temperature environment, and has good high temperature resistance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. A multi-active electrolyte, characterized in that the multi-active electrolyte comprises a first active substance and a second active substance capable of participating in electrochemical energy storage, respectively, the first active substance comprising vanadium ions;
wherein, in the case that the multi-active material electrolyte is a positive electrode electrolyte, the element of the second active material includes at least one of iron, titanium, manganese, chromium, copper, cerium, iodine, or bromine;
In the case where the multi-active material electrolyte is a negative electrode electrolyte, the element of the second active material includes at least one of iron, tin, chromium, copper, or sulfur.
2. The active material electrolyte according to claim 1, wherein in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes at least one of ferrous ions and bromide ions;
in the case where the multi-active material electrolyte is a negative electrode electrolyte, the second active material includes ferric ions.
3. The multi-active material electrolyte according to claim 1, wherein in the case where the multi-active material electrolyte is a positive electrode electrolyte, the second active material includes ferrous ions and bromide ions.
4. The multi-active material electrolyte according to claim 1, wherein the concentration of the first active material is 0.1 to 2.2mol/L and the concentration of the second active material is 0.1 to 15.0mol/L.
5. The multi-active material electrolyte according to claim 1, wherein in the case where the multi-active material electrolyte is a positive electrode electrolyte, the first active material includes at least one of trivalent vanadium ions, tetravalent vanadium ions, or pentavalent vanadium ions;
In the case where the multi-active material electrolyte is a negative electrode electrolyte, the first active material includes at least one of divalent vanadium ions, trivalent vanadium ions, or tetravalent vanadium ions.
6. The multi-active material electrolyte according to claim 5, wherein the first active material is at least one selected from the group consisting of vanadyl sulfate, vanadyl pentoxide, vanadyl bromide, and vanadyl chloride as a vanadium source.
7. The multi-active electrolyte of claim 1, further comprising a supporting electrolyte comprising at least one of hydrochloric acid, sulfuric acid, hypochlorous acid, perchloric acid, sodium chloride, potassium chloride, ammonium chloride.
8. The multi-active material electrolyte according to claim 7, wherein the supporting electrolyte comprises at least one of hydrochloric acid and sulfuric acid.
9. The multi-active material electrolyte according to claim 7or 8, wherein the supporting electrolyte provides a total hydrogen ion concentration of 0.01 to 10mol/L.
10. A flow battery comprising the multi-active electrolyte of any one of claims 1-9.
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| CN118431532A (en) * | 2024-07-03 | 2024-08-02 | 大连融科储能集团股份有限公司 | Electrolyte of iron-vanadium redox flow battery, preparation method and redox flow battery |
| CN118431532B (en) * | 2024-07-03 | 2024-10-11 | 大连融科储能集团股份有限公司 | Electrolyte of iron-vanadium redox flow battery, preparation method and redox flow battery |
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