CN112599829A - Electrolyte for flow battery and polyhalide-chromium flow battery - Google Patents

Electrolyte for flow battery and polyhalide-chromium flow battery Download PDF

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CN112599829A
CN112599829A CN202110027609.8A CN202110027609A CN112599829A CN 112599829 A CN112599829 A CN 112599829A CN 202110027609 A CN202110027609 A CN 202110027609A CN 112599829 A CN112599829 A CN 112599829A
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曾义凯
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Southwest Jiaotong University
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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
    • 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
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Abstract

The invention discloses an electrolyte for a flow battery and a polyhalide-chromium flow battery. The electrolyte for the flow battery is prepared by reacting cheap and easily-obtained chromium hydroxide with hydrochloric acid and hydrobromic acid. Before charging (the charge state is 0%), the components of the positive and negative electrolytes are consistent, and the electrolytes all contain trivalent chromium ions, chloride ions, bromide ions and hydrogen ions. The invention has the beneficial effects of providing the electrolyte for the flow battery, which has the advantages of high energy density, low cost, high charging and discharging performance, long cycle life, wide operation temperature range and the like, and has wide application prospect in the field of fixed large-scale electricity storage.

Description

Electrolyte for flow battery and polyhalide-chromium flow battery
Technical Field
The invention belongs to the field of flow batteries, and relates to an electrolyte for a flow battery and a polyhalide-chromium flow battery.
Background
The currently developed flow battery basically adopts vanadium-sulfuric acid electrolyte, and the vanadium salt required in the electrolyte is complicated in refining process, high in price, narrow in battery operation temperature range and high in heat dissipation equipment, so that the total cost of the flow battery system is high, and the large-scale popularization and application of the flow battery system are limited. The other mature electrolyte for the flow battery is a ferrochromium electrolyte, although the cost is low, the energy density is limited by the solubility of ferrous ions, the solubility is low and is only about 1.3mol/L, the ferrous/ferric pair potential is low, the output voltage of the battery is only about 1.0V, so that the energy density of the ferrochromium electrolyte is only about 17Wh/L, and the commercial development of the ferrochromium electrolyte is restricted. Therefore, the development of a novel electrolyte for a flow battery, which has high performance, low cost, easy preparation, high energy density and strong economic competitiveness, is urgently needed.
Disclosure of Invention
In this summary, concepts in a simplified form are introduced that are further described in the detailed description. This summary of the invention is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In order to solve at least part of the aforementioned technical problems, the present invention provides an electrolyte for a flow battery. The positive and negative electrolytes of the electrolyte for the flow cell are uniformly divided into aqueous solutions before charging, and both the positive and negative electrolytes contain trivalent chromium ions, chloride ions, bromide ions and hydrogen ions with the same concentration.
In the embodiment, the electrolyte for the flow battery contains 1.0-3.0mol/L of trivalent chromium ions, 1.0-6.0mol/L of bromine ions, 3.0-10.0mol/L of chlorine ions and 2.0-4.0mol/L of hydrogen ions.
In the embodiment, the electrolyte for the flow battery is prepared by taking chromium hydroxide which is a cheap and easily-obtained intermediate product in a chromium smelting process as a raw material, adding a certain amount of hydrochloric acid and hydrobromic acid, fully mixing to completely dissolve the chromium hydroxide to obtain an acidic solution of chromium-chlorine-bromine, and adding a certain amount of water. According to the scheme, the chromium hydroxide which is cheap and easy to obtain in the chromium smelting process is used as a raw material, expensive chromium chloride or chromium bromide is replaced, the processes of mother liquor concentration, crystallization, crystal crushing and the like in the preparation process of chromium chloride or chromium bromide medicines are eliminated, the preparation procedures are reduced, the cost of the chromium bromine electrolyte is obviously reduced, and the chromium bromine electrolyte has good economy.
In an embodiment, after the electrolyte for the flow battery undergoes multiple charge and discharge cycles, oxalic acid or formic acid is added to the positive electrolyte to react with the electrolyte, so as to reduce the valence state of bromine in the positive electrolyte, and the charge states of the positive electrolyte and the negative electrolyte are restored to balance.
Compared with the prior art, the invention has the advantages that: the prepared initial positive and negative electrolyte components are completely consistent (the charge state is 0%), after the chromium bromine electrolyte is charged and discharged for many times, the bromine ions and the polyhalide ions of the positive electrode can penetrate through the diaphragm and be transported to the opposite electrode to cause the battery capacity attenuation, and the problem of the battery capacity attenuation caused by the penetration of the active ions through the diaphragm can be solved by a method of mutually mixing the chromium bromine electrolytes of the positive electrode and the negative electrode and then dividing the chromium bromine electrolytes into two electrolytes of the positive electrode and the negative electrode. In addition, the chromium-bromine electrolyte solution scheme employs a halogen ion system (chloride, bromide), rather than the common sulfate ion system, with a high concentration of halogen ions. Through intensive research, the halogen ions can rapidly perform complex reaction with trivalent chromium ions at a lower temperature (about 45 ℃) to form [ Cr (H) under the condition of high-concentration halogen ions (higher than 7-9mol/L)2O)5Cl-]2+Or [ Cr (H)2O)5Br-]2+The chromium-halogen ion complex ions activate the trivalent chromium ions, effectively increase the reaction activity of the chromium ions on the cathode and greatly improve the performance of the chromium-bromine flow battery. Meanwhile, under a strong acid condition, compared with a neutral environment, bromide ions also have higher electrochemical redox activity. The operating current density of the flow battery adopting the electrolyte solution scheme can reach 400mA cm-2And meanwhile, the charging and discharging energy efficiency is kept above 80%.
Compared with the prior art, the invention also has the advantages that: the electrolyte solution has a low price and good chemical stability. Compared with a common sulfuric acid electrolyte system, the chromium-bromine electrolyte system has the advantage of remarkably reduced viscosity, which is beneficial to reducing the pumping power loss of the flow battery. The reasonable design of the chromium-bromine electrolyte enables the output voltage of the corresponding chromium-bromine flow battery to reach 1.3V, the operation temperature range is wide, the battery can safely operate at-10 to 70 ℃, the performance of the battery is excellent, and the energy density of the electrolyte reaches 41 Wh/L; vanadium pentoxide can be separated out when the operating temperature of the vanadium-sulfuric acid electrolyte adopted by the all-vanadium redox flow battery exceeds 40 ℃, and expensive and complicated heat dissipation equipment is required, so that the application of the vanadium-sulfuric acid electrolyte is limited. In addition, the price of active substances such as chromium hydroxide, hydrobromic acid and the like is far lower than that of active substances such as vanadium pentoxide or vanadyl sulfate and the like required by the preparation of the vanadium-sulfuric acid electrolyte. Chromium bromine electrolyte costs only $ 28 per kilowatt-hour, while vanadium-sulfuric acid electrolyte costs up to $ 90 per kilowatt-hour.
The invention also provides a polyhalide-chromium flow battery, which adopts the electrolyte for the flow battery as a positive electrolyte and a negative electrolyte, and comprises an electrochemical reaction battery, a positive electrolyte storage tank, a positive electrolyte, a negative electrolyte storage tank, a negative electrolyte, a capacity regeneration device, a driving device and a circulating pipeline; the electrochemical reaction pool is formed by connecting one or more monocells in series, each monocell comprises a positive current collector, a positive electrode, a diaphragm, a negative electrode and a negative current collector, and a negative electrode electrolyte contains a negative redox couple Br-/Br2Cl-The anode electrolyte contains anode oxidation-reduction couple divalent chromium ions/trivalent chromium ions.
In an embodiment, the anolyte and catholyte are delivered to the anode and cathode from anolyte and catholyte reservoirs via pumps, respectively, during charging, with Br in the anolyte-Oxidation of ions to Br at the anode2Cl-Multiple halide ions, wherein trivalent chromium ions in the negative electrode electrolyte are reduced into divalent chromium ions at the negative electrode; at the time of discharge, Br2Cl-Reduction of polyhalide ion to Br at positive electrode-The ions are dissolved in the electrolyte of the anode and are returned to the anode liquid storage tank through the pump, and the bivalent chromium ions are oxidized into trivalent chromium ions at the cathode and are dissolved in the electrolyte of the cathode and are returned to the cathode liquid storage tank through the pump.
Drawings
The following drawings of the invention are included to provide a further understanding of the invention. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles and apparatus of the invention.
FIG. 1 is a charge-discharge curve diagram of a chromium-bromine electrolyte prepared according to an embodiment of the present invention in a chromium-bromine flow battery;
FIG. 2 is a graph showing the cycle characteristics of a chromium bromine electrolyte prepared according to an example of the present invention in a chromium bromine flow battery;
FIG. 3 is a schematic diagram of a cell of a polyhalide-chromium flow battery provided by the present invention;
FIG. 4 is a graph of the charge and discharge curves of a polyhalide-chromium flow battery prepared in an example of the invention;
FIG. 5 is a graph of operating current density versus efficiency for a polyhalide-chromium flow battery prepared in an example of the invention;
FIG. 6 shows a cell prepared according to an example of the present invention at a current density of 500mA cm-2Cyclic characteristic diagram of time.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
In the following description, for purposes of explanation, specific details are set forth in order to provide a thorough understanding of the present invention. It is apparent that the practice of the invention is not limited to the specific details set forth herein as are known to those of skill in the art. The following detailed description of the preferred embodiments of the present invention, however, the present invention may have other embodiments in addition to the detailed description, and should not be construed as being limited to the embodiments set forth herein.
In the following, specific embodiments of the present invention will be described in more detail with reference to the accompanying drawings, which illustrate representative embodiments of the invention and do not limit the invention.
The first embodiment is as follows:
the electrolyte for the flow battery can be a chromium bromine electrolyte. The preparation scheme of the electrolyte comprises the steps of adopting 2.0mol of Cr (OH)3Reacting with 6.0mol of hydrochloric acid and 3.0mol of hydrobromic acid, fully stirring to completely dissolve chromium hydroxide, and adding a certain amount of purified water to prepare 2.0mol/L CrCl3And 1.0L of +3.0mol/L HBr chromium bromine electrolyte, taking a certain amount of the chromium bromine electrolyte as positive and negative electrolyte respectively, and putting the positive and negative electrolyte into the chromium-bromine flow battery for charge and discharge tests.
During charging, the positive electrolyte and the negative electrolyte are respectively delivered to the positive electrode and the negative electrode from the positive electrolyte storage tank and the negative electrolyte storage tank, trivalent chromium ions in the negative electrolyte are reduced into divalent chromium ions at the negative electrode, the divalent chromium ions are dissolved in the negative electrolyte, and Br in the positive electrolyte-Oxidation to Br at the positive electrode2Cl-Ions are dissolved in the positive electrolyte; upon discharge, the process reverses.
The single cell of the chromium-bromine flow battery adopting the chromium-bromine electrolyte is 400mA cm-2The constant current charge-discharge curve under current density is shown in figure 1, the cycle characteristic is shown in figure 2, and the result shows that the current density is 400mAcm-2Under the condition, the energy efficiency reaches 82 percent, and the coulombic efficiency is higher than 96 percent.
Example two:
this example provides a chromium-bromine electrolyte for a chromium-bromine flow battery, which is prepared by reacting 4.8mol of chromium hydroxide with 15.4mol of hydrochloric acid and 4.0mol of hydrobromic acid, stirring sufficiently to completely dissolve the chromium hydroxide, and adding a certain amount of clear water to obtain 2.4mol/L of CrCl3+0.5mol/L HCl +2.0mol/L HBr chromium bromine electrolyte 2.0L, divided into positive and negative electrode chromium bromine electrolytes each 1.0L, put into chromium bromine flow battery to charge and discharge. The results show that the current density of the single chromium-bromine flow battery cell adopting the chromium-bromine electrolyte is 300mA cm-2Under the condition, the energy efficiency reaches 85 percent, and the coulombic efficiency is higher than 95 percent.
As the battery cycle progresses, the negative trivalent chromium ions are accompanied by hydrogen evolution reaction during charging, which causes the positive electrolyte charge state of the battery to be higher than that of the negative electrolyte, resulting in the reduction of the battery capacity. After the anode electrolyte is subjected to multiple charge-discharge cycles, oxalic acid or formic acid is added periodically or aperiodically to react with the accumulated bromine in the anode electrolyte to generate hydrogen bromide and carbon dioxide. And the carbon dioxide gas is discharged out of the liquid storage tank after condensation and backflow, so that the charge states of the positive electrolyte and the negative electrolyte of the battery return to a consistent state, and further the capacity of the battery is recovered, and the electrolyte can be repeatedly used for a long time. The reaction equation for reducing the bromine valence state of the positive electrolyte is as follows:
Br2+C2O4H2→2HBr+2CO2↑
or:
Br2+CO2H2→2HBr+CO2↑
compared with the prior art, the invention also has the advantages that: the chromium ions and the bromine ions have good electrochemical oxidation-reduction activity in a chromium-bromine electrolyte system, and have low price and good chemical stability. The components of the positive and negative electrolytes are consistent before charging, and the electrolytes can be separated again by mixing the positive and negative electrolytes after multiple charging and discharging, so that the problem of capacity loss caused by penetration of chromium ions and bromine ions through the diaphragm is solved. Compared with a common sulfuric acid electrolyte system, the chromium-bromine electrolyte system has the advantage of remarkably reduced viscosity, which is beneficial to reducing the pumping power loss of the flow battery. The reasonable design of the chromium-bromine electrolyte ensures that the output voltage of the corresponding chromium-bromine flow battery can reach 1.3V, and the operating current density of the battery reaches 400mA cm-2Meanwhile, the charging and discharging energy efficiency is kept above 80%, the operation temperature range is wide, the battery can safely operate at minus 10 to 70 ℃, and the battery performance is excellent; vanadium pentoxide can be separated out when the operating temperature of the vanadium-sulfuric acid electrolyte adopted by the all-vanadium redox flow battery exceeds 40 ℃, and expensive and complicated heat dissipation equipment is required, so that the application of the vanadium-sulfuric acid electrolyte is limited. In addition, the price of active substances such as chromium hydroxide, hydrobromic acid and the like is far lower than that of active substances such as vanadium pentoxide or vanadyl sulfate and the like required by the preparation of the vanadium-sulfuric acid electrolyte. Chromium bromine electrolyte costs only $ 28 per kilowatt-hour, while vanadium-sulfuric acid electrolyte costs up to $ 90 per kilowatt-hour.
The bromine ions and the chromium ions adopted by the battery have higher solubility, wherein the chromium ions with relatively lower solubility can also easily realize the dissolution of 2.5mol/L, and the energy density of the electrolyte can reach 41Wh/L by adding the higher battery output voltage of 1.3V, which is obviously higher than the energy density (17Wh/L) of the iron-chromium electrolyte adopted by the iron-chromium flow battery, so that the whole power storage system is more compact and the construction cost is lower.
The polyhalide-chromium flow battery comprises an electrochemical reaction battery, electrolyte and a circulating pipeline system; the electrochemical reaction cell is a single cell or a plurality of single cells which form a series structure on a circuit, as shown in fig. 1, each single cell comprises a positive electrode 1, a diaphragm 2, a negative electrode 3, a positive electrode current collector 4 and a negative electrode current collector 5, and each single cell is divided into a positive electrode side and a negative electrode side which are independent of each other by the diaphragm 2; the anode side and the anode electrolyte storage tank 6 form a closed loop, and the anode electrolyte in the anode electrolyte storage tank 6 contains Br-Under the action of the positive electrode side driving pump 8, the positive electrolyte circularly flows through the positive porous electrode through the positive electrode side pipeline 10 to participate in chemical reaction to form a positive electrode half cell; the negative electrode side and the negative electrolyte storage tank 7 form a closed loop, the negative electrolyte in the negative electrolyte storage tank 7 is an active substance containing trivalent chromium ions, and the negative electrolyte of the positive electrolyte circularly flows through the negative porous electrode through the negative pipeline 11 under the action of the negative electrode side driving pump 9 to participate in chemical reaction to form a negative half cell; the positive and negative pole reaction mechanism of the polyhalide-chromium flow battery is specifically shown as the following formula:
and (3) positive pole reaction:
Figure BDA0002890906610000061
E0＝+0.99V vs.SHE(Eq.1a)
and (3) cathode reaction:
Figure BDA0002890906610000062
E0＝-0.31V vs.SHE(Eq.1b)
and (3) total reaction:
Figure BDA0002890906610000063
E0＝1.30V(Eq.1c)
during charging, the positive electrolyte and the negative electrolyte are respectively delivered to the positive electrode and the negative electrode from the positive electrolyte storage tank and the negative electrolyte storage tank, trivalent chromium ions in the negative electrolyte are reduced into divalent chromium ions at the negative electrode, the divalent chromium ions are dissolved in the negative electrolyte, and Br in the positive electrolyte-Oxidation to Br at the positive electrode2Cl-Multiple halide ions are dissolved in the positive electrolyte; upon discharge, the process reverses.
Example three:
this example provides a polyhalide-chromium flow battery and electrochemical performance testing was performed thereon:
a method for preparing a polyhalide-chromium flow battery, comprising the steps of;
the method comprises the following steps: electrolyte preparation:
anode electrolyte: 25mL of an aqueous solution containing 3mol/L HBr and 1mol/L CrCl3。
And (3) cathode electrolyte: 25mL of an aqueous solution containing 3mol/L HBr and 1mol/L CrCl3。
Step two: assembling the battery:
the structure and the system of the single cell are shown in figure 3, and the current collector and the anode (2 multiplied by 2 cm) are arranged from left to right in sequence2Carbon cloth), diaphragm (Nafion HP), negative electrode (2X 2 cm)2Carbon cloth), a negative current collector;
step three: and (3) testing the battery:
at 55 degrees Celsius, the cells were at 300, 400, 500 and 600mA/cm2The constant current charge-discharge curve under current density is shown in figure 4, the operation current density-efficiency curve is shown in figure 5, and the result shows that the current density is 600mAcm-2Under the condition, the energy efficiency reaches 81.2 percent, and the coulombic efficiency is higher than 97 percent.
Example four:
this example provides a polyhalide-chromium flow battery and electrochemical performance testing was performed thereon:
a method for preparing a polyhalide-chromium flow battery, comprising the steps of;
the method comprises the following steps: electrolyte preparation:
anode electrolyte: 20mL of an aqueous solution containing 2.5mol/L HBr and 1mol/L CrCl3。
And (3) cathode electrolyte: 20mL of an aqueous solution containing 2.5mol/L HBr and 1mol/L CrCl3。
Step two: assembling the battery:
the structure and the system of the single cell are shown in figure 3, and the current collector 4 and the anode 1(2 multiplied by 2 cm) are arranged from left to right in sequence2Carbon cloth), separator 2(Nafion HP), negative electrode 3(2 × 2 cm)2Carbon cloth), negative current collector 5;
step three: and (3) testing the battery:
at 45 ℃, the single cell is at 500mA/cm2The constant current charge and discharge cycle under the current density is 600 times, the cycle characteristic diagram is shown in figure 6, and it can be seen from figure 6 that the coulombic efficiency and the energy efficiency of the battery are kept stable in 600 cycles.
As the battery cycle progresses, the negative trivalent chromium ions are accompanied by hydrogen evolution reaction during charging, which causes the positive electrolyte charge state of the battery to be higher than that of the negative electrolyte, resulting in the reduction of the battery capacity. The capacity regeneration device is a hydrogen-bromine gas phase photo-thermal reactor, is provided with a visible light source and an electric heating wire heater, has the operation temperature of 60-600 ℃, and has the function of recovering the capacity of the battery. The capacity regeneration device can carry out chemical combination reaction on hydrogen generated by hydrogen evolution reaction of the negative electrode and bromine steam evaporated by the positive electrode liquid storage tank under the conditions of illumination and heating to generate hydrogen bromide, so that the charge states of the positive and negative electrodes of the battery electrolyte return to a consistent state, and the capacity of the battery is recovered.
The specific workflow and construction are shown in fig. 3. The accumulated hydrogen/nitrogen mixed gas in the cathode reservoir 7 is delivered to the hydrogen-bromine gas phase reactor 15 by the first gas pump 12 and the gas line 13. The bromine vapor/nitrogen mixed gas in the anode reservoir 6 is fed to the hydrogen-bromine vapor gas phase reactor 15 through the second gas pump 14 and the circuit 15. The hydrogen and bromine vapor are subjected to chemical combination reaction in a gas phase reactor 15 under the temperature rise action of an electric heating wire heater 16 and the catalytic action of a visible light illuminator 17 to generate hydrogen bromide, and the hydrogen bromide is condensed at the bottom of the reactor and returns to the anode liquid storage tank 6 along with the loop 15. Excess hydrogen is returned to the negative reservoir 7 along line 13. The chemical reaction formula is as follows:
Figure BDA0002890906610000081
by this capacity recovery apparatus, the capacity of the polyhalide-chromium flow battery can be recovered on-line, as shown in fig. 6.
The positive redox couple of the polyhalide-chromium flow battery of the invention is Br-/Br2Cl-The negative electrode redox couple is divalent chromium ion/trivalent chromium ion, the positive and negative half cells are separated into mutually independent positive and negative electrode sides by a diaphragm, the positive and negative electrode sides respectively form a closed loop with two sides of electrolyte storage tanks, and the electrolytes circularly flow through respective porous electrodes under the action of a driving device to participate in electrochemical reaction. During charging, trivalent chromium ions obtain an electron on the negative electrode to be reduced into divalent chromium ions, and two Br on the positive electrode-Each ion losing one electron to Br2Cl-A polyhalide ion; during discharge, Br is generated at the positive electrode and the negative electrode respectively, contrary to the charging process-Ions and divalent chromium ions. The discharge products of the redox couple of the negative electrode are dissolved in the electrolyte, so that the full liquid flow battery is provided.
Compared with the prior art, the invention also has the advantages that: by adopting the electrolyte scheme, a polyhalide-chromium flow battery system is provided, wherein a cathode redox couple in the battery system is divalent chromium ions/trivalent chromium ions, and an anode redox couple in the battery system is Br-/Br2Cl-The positive and negative redox couples have good electrochemistry on a given electrodeRedox activity, low cost and good chemical stability. The output voltage of the flow battery obtained by reasonably selecting and constructing the polyhalide/chromium couple can reach 1.3V, and the operating current density of the battery reaches 600mA cm-2Meanwhile, the charging and discharging energy efficiency is kept above 81%, the operation temperature range is wide, the battery can safely operate at minus 10 to 70 ℃, and the battery performance is excellent; and when the operation temperature of the all-vanadium redox flow battery exceeds 40 ℃, vanadium pentoxide can be separated out, and the application of the all-vanadium redox flow battery is limited. In addition, the price of active substances such as chromium chloride, hydrobromic acid and the like is far lower than that of active substances such as vanadium pentoxide or vanadyl sulfate and the like used in the all-vanadium flow battery. The polyhalide-chromium flow battery electrolyte costs only $ 28 per kilowatt-hour, while the all-vanadium flow battery electrolyte costs up to $ 90 per kilowatt-hour. The battery of the invention adopts the halogen ions and the chromium ions with higher solubility, wherein the chromium ions with relatively lower solubility can also realize the dissolution of 2.5mol/L relatively easily, and the energy density of the electrolyte can reach 41Wh/L by adding the higher output voltage of the battery of 1.3V, which is obviously higher than that of the electrolyte of the all-vanadium redox flow battery and the ferrochrome redox flow battery.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Terms such as "part," "member," and the like, when used herein, can refer to either a single part or a combination of parts. Terms such as "mounted," "disposed," and the like, as used herein, may refer to one component as being directly attached to another component or one component as being attached to another component through intervening components. Features described herein in one embodiment may be applied to another embodiment, either alone or in combination with other features, unless the feature is otherwise inapplicable or otherwise stated in the other embodiment.
The present invention has been described in terms of the above embodiments, but it should be understood that the above embodiments are for purposes of illustration and description only and are not intended to limit the invention to the scope of the described embodiments. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications fall within the scope of the present invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. An electrolyte for a flow battery, characterized in that: the positive and negative electrolytes of the electrolyte for the flow battery are uniformly divided before charging, and contain trivalent chromium ions, chloride ions, bromide ions and hydrogen ions.
2. The electrolyte for a flow battery according to claim 1, wherein: the electrolyte for the flow battery contains 1.0-3.0mol/L of trivalent chromium ions, 1.0-6.0mol/L of bromide ions, 3.0-10.0mol/L of chloride ions and 2.0-4.0mol/L of hydrogen ions.
3. The electrolyte for a flow battery according to claim 1 or 2, wherein: the electrolyte for the flow battery is prepared by reacting chromium hydroxide obtained in a chromium smelting process with hydrochloric acid and hydrobromic acid.
4. The electrolyte for a flow battery according to any one of claims 1-3, wherein: after the electrolyte for the flow battery is subjected to multiple charge-discharge cycles, oxalic acid or formic acid is added into the positive electrolyte to react with the electrolyte so as to reduce the valence state of bromine in the electrolyte, and the charge states of the positive electrolyte and the negative electrolyte are restored to be balanced.
5. A polyhalide-chromium flow cell, its special feature isCharacterized in that: the polyhalide-chromium flow battery uses the electrolyte for the flow battery as claimed in claims 1 to 4 as a positive electrolyte and a negative electrolyte, and comprises an electrochemical reaction cell, a positive electrolyte storage tank, a positive electrolyte, a negative electrolyte storage tank, a negative electrolyte, a capacity regeneration device, a driving device and a circulation pipeline; the electrochemical reaction pool is formed by connecting one or more monocells in series, each monocell comprises a positive current collector, a positive electrode, a diaphragm, a negative electrode and a negative current collector, and a negative electrode electrolyte contains a negative redox couple Br-/Br2Cl-The anode electrolyte contains anode oxidation-reduction couple divalent chromium ions/trivalent chromium ions.
6. The polyhalide-chromium flow battery as in claim 5, wherein said anolyte and catholyte are pumped from anolyte and catholyte reservoirs to the anode and cathode, respectively, upon charging, Br in the anolyte-Oxidation of ions to Br at the anode2Cl-Multiple halide ions, wherein trivalent chromium ions in the negative electrode electrolyte are reduced into divalent chromium ions at the negative electrode; at the time of discharge, Br2Cl-Reduction of polyhalide ion to Br at positive electrode-The ions are dissolved in the electrolyte of the anode and are returned to the anode liquid storage tank through the pump, and the bivalent chromium ions are oxidized into trivalent chromium ions at the cathode and are dissolved in the electrolyte of the cathode and are returned to the cathode liquid storage tank through the pump.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102479968A (en) * 2010-11-29 2012-05-30 中国科学院大连化学物理研究所 Zinc / polyhalide energy storage cell
CN102640346A (en) * 2009-10-23 2012-08-15 红流私人有限公司 Recombinator for flowing electrolyte battery
US20180019483A1 (en) * 2016-07-13 2018-01-18 University Of Tennessee Research Foundation Redox flow battery with increased-surface-area electrode and asymmetric electrolyte concentration
CN108134120A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery method for restoring performance
CN109988922A (en) * 2018-01-03 2019-07-09 唐翔 Ferrochrome liquid phase method manufactures high-purity metal chromium co-producing bio medical material technique

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4469760A (en) * 1981-09-08 1984-09-04 Electric Power Research, Institute Redox battery including a bromine positive electrode and a chromium ion negative electrode, and method
CN101213700B (en) * 2005-06-20 2012-11-21 新南创新私人有限公司 Improved perfluorinated membranes and improved electrolytes for redox cells and batteries
WO2011149624A1 (en) * 2010-05-24 2011-12-01 Ecovoltz, Inc. Secondary battery system
CN102790233A (en) * 2011-05-20 2012-11-21 罗臬 Flow battery
JP6475986B2 (en) * 2011-09-28 2019-02-27 ユナイテッド テクノロジーズ コーポレイションＵｎｉｔｅｄ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｒｐｏｒａｔｉｏｎ Flow battery with two-phase storage
AU2013274244A1 (en) * 2012-06-15 2014-12-18 University Of Delaware Multiple-membrane multiple-electrolyte redox flow battery design
JP6400577B2 (en) * 2012-07-27 2018-10-03 ロッキード マーティン エナジー, エルエルシーLockheed Martin Energy, Llc Optimal membrane electrochemical energy storage system
WO2016154195A1 (en) * 2015-03-24 2016-09-29 3M Innovative Properties Company Porous electrodes and electrochemical cells and liquid flow batteries therefrom
PT3320576T (en) * 2015-07-08 2022-02-08 Agora Energy Tech Ltd Redox flow battery with carbon dioxide based redox couple
JP2019067702A (en) * 2017-10-04 2019-04-25 日立化成株式会社 Secondary battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102640346A (en) * 2009-10-23 2012-08-15 红流私人有限公司 Recombinator for flowing electrolyte battery
CN102479968A (en) * 2010-11-29 2012-05-30 中国科学院大连化学物理研究所 Zinc / polyhalide energy storage cell
US20180019483A1 (en) * 2016-07-13 2018-01-18 University Of Tennessee Research Foundation Redox flow battery with increased-surface-area electrode and asymmetric electrolyte concentration
CN108134120A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery method for restoring performance
CN109988922A (en) * 2018-01-03 2019-07-09 唐翔 Ferrochrome liquid phase method manufactures high-purity metal chromium co-producing bio medical material technique

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