CN114628754B - All-vanadium redox flow battery electrolyte containing nitroimidazole additive and application thereof - Google Patents

All-vanadium redox flow battery electrolyte containing nitroimidazole additive and application thereof Download PDF

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CN114628754B
CN114628754B CN202011455858.9A CN202011455858A CN114628754B CN 114628754 B CN114628754 B CN 114628754B CN 202011455858 A CN202011455858 A CN 202011455858A CN 114628754 B CN114628754 B CN 114628754B
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electrolyte
additive
vanadium
battery
redox flow
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CN114628754A (en
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孙佳伟
李先锋
张华民
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M2300/0011—Sulfuric acid-based
    • 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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Sustainable Energy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses an electrolyte of an all-vanadium redox flow battery containing a nitroimidazole additive and application thereof, and belongs to the technical field of energy storage of all-vanadium redox flow batteries. The nitro-containing additive is one or more than two of metronidazole, 1- (3-chloro-2-hydroxypropyl) -2-methyl-5-nitroimidazole, dimethylnitroimidazole and metronidazole: the concentration of the additive is 0.01 g/L-5 g/L. The additive used in the invention contains nitro and imidazole, which can inhibit the capacity attenuation generated when the battery operates under high temperature condition, improve the battery performance, and improve the solubility of vanadium ions and the battery energy density. The invention has simple process operation, energy conservation, environmental protection and low cost, and can realize the stable operation of the electrolyte in the battery.

Description

All-vanadium redox flow battery electrolyte containing nitroimidazole additive and application thereof
Technical Field
The invention belongs to the technical field of energy storage of all-vanadium redox flow batteries, and particularly relates to an all-vanadium redox flow battery electrolyte containing a nitroimidazole additive and application thereof.
Background
With the continuous exhaustion of fossil energy and the continuous enhancement of environmental protection consciousness of people worldwide, renewable energy power generation technology is increasingly favored by people. Renewable energy sources mainly comprise wind energy, solar energy, biomass energy, ocean energy and the like. These renewable energy sources have significant discontinuities and instability. In order to smooth and stabilize the power generation output of renewable energy sources, efficient energy storage technologies must be developed. The all-vanadium redox flow battery (VFB) has the outstanding advantages of independent and adjustable system capacity and power, quick response, safety, reliability, environmental friendliness, long cycle life, easiness in maintenance and regeneration and the like, so that the all-vanadium redox flow battery (VFB) becomes one of the most promising technologies in large-scale energy storage of power grid peak clipping and valley filling, emergency and standby power stations and the like.
The electrolyte is an important component of the all-vanadium redox flow battery, and the concentration and the volume of the electrolyte directly determine the energy density and the capacity of the battery. The use concentration of vanadium ions in the electrolyte system is generally not higher than 2M, the energy density is low, and after the concentration is further increased, the concentration of vanadium ions on one side is easily increased due to the mutual strings of vanadium ions in the running process of the battery, so that the vanadium ions are separated out, and the stability of the battery is further reduced; and secondly, after the temperature of the battery is increased, the pentavalent vanadium in the positive electrode electrolyte can be separated out into vanadium pentoxide solid, so that the capacity of the battery is reduced, and meanwhile, the separated solid can block the battery, so that the battery cannot continue to operate. Therefore, to increase the energy density, the stability of the high-concentration electrolyte must be improved, and at the same time, the stability control of the electrolyte (especially the high-concentration pentavalent vanadium ions) at high temperature plays a decisive role in the stable and reliable operation of the battery, which is also the focus of attention of many researchers.
Disclosure of Invention
The invention aims to solve the problems and provides an electrolyte of an all-vanadium redox flow battery containing a nitroimidazole additive, so as to achieve the purpose of high-efficiency and stable operation of the all-vanadium redox flow battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the electrolyte of the positive electrode and the negative electrode of the all-vanadium redox flow battery are the same, and the electrolyte of the all-vanadium redox flow battery contains an additive with nitro and imidazole, wherein the additive comprises one, two or more than two of metronidazole, 1- (3-chloro-2-hydroxypropyl) -2-methyl-5-nitroimidazole, dimethylnitroimidazole and metronidazole; the additive is added into the electrolyte, and the concentration of the additive in the electrolyte is 0.01 g/L-5 g/L.
Further, the preferable concentration of the additive in the electrolyte is 0.1g/L to 2g/L.
Further, the additive is preferably 1- (3-chloro-2-hydroxypropyl) -2-methyl-5-nitroimidazole.
Further, the electrolyte is an aqueous solution containing one or two of vanadium ions and vanadyl and sulfate radical, the concentration of vanadium element in the aqueous solution of the electrolyte is 0.5-5 mol/L, and the sulfate radical (containing SO) 4 2- And HSO 4 - ) The concentration of (C) is 1-6 mol/L.
Further, the preferable concentration of vanadium element in the aqueous solution of the electrolytic solution is 1 to 4mol/L, more preferably 2 to 4mol/L, and the preferable concentration of sulfate radical is 2 to 4mol/L.
The application of the electrolyte in the vanadium redox flow battery as the battery electrolyte.
Further, the method is applied to positive and negative electrolytes in all-vanadium redox flow batteries.
The additive used in the invention contains nitro and imidazole, which can inhibit the capacity attenuation generated when the battery operates under high temperature condition, improve the battery performance, and improve the solubility of vanadium ions and the battery energy density. The invention has simple process operation, energy conservation, environmental protection and low cost, and can realize the stable operation of the electrolyte in the battery.
The beneficial results of the invention are:
1) The additive used in the invention can inhibit capacity attenuation generated when the battery is operated under high temperature condition, and improve the battery performance.
2) The additive used in the invention can also improve the solubility of vanadium ions and improve the energy density of the battery.
3) The invention has simple process operation, energy conservation, environmental protection and low cost, and can ensure that the battery can operate efficiently and stably for a long time.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Comparative example 1
Preparing electrolyte for single cell experiments, wherein the concentration of vanadium element in the electrolyte is 1.5M, the ratio of V (III) to V (IV) is 1:1, the concentration of sulfuric acid is 3M, the diaphragm is Nafion115, the electrode is carbon felt, and the electrode area is 48cm 2 The volume of the electrolyte of the positive electrode and the negative electrode is 100mL, and the current density is 80mA/cm 2 . The charge-discharge voltage interval is 1-1.55V.
The average performance of 100 cycles is 95% of coulomb efficiency, 82% of voltage efficiency and 78% of energy efficiency under test at normal temperature. After 100 cycles, the electrolyte capacity decays 45%.
The average performance of 100 cycles was 90% coulombic efficiency, 78% voltage efficiency and 70% energy efficiency when tested in an environment at 50 ℃. After 100 cycles, the electrolyte capacity decays by 70%.
Comparative example 2
Single cell experiments were performed by preparing an electrolyte containing an imidazole additive, wherein the electrolyte has a vanadium element concentration of 1.5M, V (III) andv (IV) ratio is 1:1, sulfuric acid concentration is 3M, imidazole concentration is 1g/L, membrane is Nafion115, electrode is carbon felt, electrode area is 48cm 2 The volume of the electrolyte of the positive electrode and the negative electrode is 100mL, and the current density is 80mA/cm 2 . The charge-discharge voltage interval is 1-1.55V.
The average performance of 100 cycles is 96% of coulombic efficiency, 85% of voltage efficiency and 82% of energy efficiency, and the electrolyte capacity decays by 42% after 100 cycles.
The average performance of 100 cycles is 92% of coulomb efficiency, 84% of voltage efficiency, 77% of energy efficiency and 52% of electrolyte capacity decay after 100 cycles under 50 ℃ environment.
Comparative example 3
A single cell experiment is carried out by preparing electrolyte containing nitrotoluene additive, wherein the concentration of vanadium element in the electrolyte is 1.5M, the ratio of V (III) to V (IV) is 1:1, the concentration of sulfuric acid is 3M, the concentration of nitrotoluene is 0.3g/L, the diaphragm is Nafion115, the electrode is carbon felt, and the electrode area is 48cm 2 The volume of the electrolyte of the positive electrode and the negative electrode is 100mL, and the current density is 80mA/cm 2 . The charge-discharge voltage interval is 1-1.55V.
The average performance of 100 cycles was tested to be 96% coulombic efficiency, 84% voltage efficiency, 81% energy efficiency, and 44% electrolyte capacity decay after 100 cycles.
The average performance of 100 cycles is 90% of coulomb efficiency, 79% of voltage efficiency, 71% of energy efficiency and 68% of electrolyte capacity decay after 100 cycles under 50 ℃ environment.
Comparative example 4
819g of vanadyl sulfate solids are weighed out and added to 1L of an aqueous solution containing 3M sulfuric acid, after stirring for 3 hours, the vanadyl sulfate solids are found to remain insoluble. The electrolyte of the all-vanadium redox flow battery cannot be configured.
Comparative example 5
819g of vanadyl sulfate solids and 2g of imidazole are weighed and added to 1L of an aqueous solution containing 3M sulfuric acid, and after stirring for 3 hours, the vanadyl sulfate solids are dissolved. Then, the electrolyte was divided into two parts, one part was left at room temperature, the other part was charged as a positive electrode, and after charging to soc=80%, the electrolyte was placed in a water bath at 50 ℃, the state of the two parts was observed, and the stabilization time was recorded, and the results are shown in table 2.
Comparative example 6
819g of vanadyl sulfate solid and 2g of nitrotoluene were weighed and added to 1L of an aqueous solution containing 3M sulfuric acid, and after stirring for 3 hours, the vanadyl sulfate solid was dissolved. Then, the electrolyte was divided into two parts, one part was left at room temperature, the other part was charged as a positive electrode, and after charging to soc=80%, the electrolyte was placed in a water bath at 50 ℃, the state of the two parts was observed, and the stabilization time was recorded, and the results are shown in table 2.
Examples 1 to 5
Single cell experiments are carried out by preparing electrolyte containing nitroimidazole additives, wherein the concentration of vanadium element in the electrolyte is 1.5M, the ratio of V (III) to V (IV) is 1:1, the concentration of sulfuric acid is 3M, the types and the concentrations of the additives are shown in Table 1, the diaphragm is Nafion115, the electrode is carbon felt, and the electrode area is 48cm 2 The volume of the electrolyte of the positive electrode and the negative electrode is 100mL, and the current density is 80mA/cm 2 . The charge-discharge voltage interval is 1-1.55V. The test results are shown in Table 1 after normal temperature test and high temperature test.
Table 1 detailed experimental parameters and battery performances of examples 1 to 5 and comparative examples 1 to 3
As can be seen from table 1, after the nitroimidazole additive is added, the battery performance is greatly improved compared with that of a blank test (comparative example 1), the imidazole additive or the nitrotoluene additive, which indicates that the additive can improve the battery performance. Meanwhile, the high-temperature capacity attenuation at 50 ℃ is obviously reduced compared with that of a blank test, an imidazole additive or a nitrotoluene additive, which shows that the additive can improve the stability of the electrolyte.
Examples 6 to 7
819g of vanadyl sulfate solid and 2g of nitroimidazole additives (the types and the concentrations of the additives are shown in Table 2) are weighed and added into 1L of aqueous solution containing 3M sulfuric acid, and after stirring for 3 hours, the vanadyl sulfate solid is found to be completely dissolved, so that the electrolyte of the all-vanadium redox flow battery can be prepared. Then, the electrolyte was divided into two parts, one part was left at room temperature, the other part was charged as a positive electrode, and after charging to soc=80%, the electrolyte was placed in a water bath at 50 ℃, the state of the two parts was observed, and the stabilization time was recorded, and the results are shown in table 2.
TABLE 2 static test data at high concentration and high temperature for examples 6-7 and comparative examples 5-6
As can be seen from Table 2, in comparative example 4, the vanadyl sulfate was not completely dissolved, and the imidazole additive or nitrotoluene additive was added, and although the vanadyl sulfate was completely dissolved, the stability at normal temperature and the stability at high temperature were not high, and solids were precipitated in a short period of time. After the nitroimidazole additive is added, vanadyl sulfate is completely dissolved, and the electrolyte has higher stability time, and is stable for more than 30 days at normal temperature and more than 3 days at 50 ℃. It is demonstrated that the nitroimidazole additive can improve the concentration and stability of the electrolyte.

Claims (7)

1. An all-vanadium redox flow battery electrolyte, which is characterized in that: the electrolyte of the all-vanadium redox flow battery contains an additive with nitro and imidazole, wherein the additive comprises one, two or more than two of metronidazole, 1- (3-chloro-2-hydroxypropyl) -2-methyl-5-nitroimidazole, dimethylnitroimidazole and metronidazole; the additive is added into the electrolyte, and the concentration of the additive in the electrolyte is 0.01 g/L-5 g/L.
2. The all-vanadium redox flow battery electrolyte of claim 1, wherein: the concentration of the additive in the electrolyte is 0.1 g/L-2 g/L.
3. The all-vanadium redox flow battery electrolyte of claim 1, wherein: the electrolyte is an aqueous solution containing one or two of vanadium ions and vanadium oxygen radicals and sulfate radical, wherein the concentration of vanadium element in the aqueous solution of the electrolyte is 0.5-5 mol/L, and the concentration of sulfate radical is 1-6 mol/L.
4. An all vanadium flow battery electrolyte according to claim 3, wherein the sulfate comprises SO 4 2- And HSO 4 - 。
5. The all-vanadium redox flow battery electrolyte of claim 1 or 3, wherein: the concentration of vanadium element in the aqueous solution of the electrolyte is 1-4 mol/L, and the concentration of sulfate radical is 2-4 mol/L.
6. Use of the electrolyte according to any one of claims 1-5 as battery electrolyte in an all-vanadium flow battery.
7. The use according to claim 6, for positive and negative electrolytes in all-vanadium flow batteries.
CN202011455858.9A 2020-12-10 2020-12-10 All-vanadium redox flow battery electrolyte containing nitroimidazole additive and application thereof Active CN114628754B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0864223A (en) * 1994-08-22 1996-03-08 Sumitomo Electric Ind Ltd Electrolyte for vanadium redox flow type battery
CN109768325A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 A kind of positive electrolyte for all-vanadiumredox flow battery and its application containing additive
CN110734515A (en) * 2019-09-25 2020-01-31 中盐金坛盐化有限责任公司 imidazole iron polymer, synthetic method, battery and battery system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0864223A (en) * 1994-08-22 1996-03-08 Sumitomo Electric Ind Ltd Electrolyte for vanadium redox flow type battery
CN109768325A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 A kind of positive electrolyte for all-vanadiumredox flow battery and its application containing additive
CN110734515A (en) * 2019-09-25 2020-01-31 中盐金坛盐化有限责任公司 imidazole iron polymer, synthetic method, battery and battery system

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