CN111509247A - Method for regenerating electrolyte of failure vanadium battery - Google Patents

Method for regenerating electrolyte of failure vanadium battery Download PDF

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CN111509247A
CN111509247A CN202010261124.0A CN202010261124A CN111509247A CN 111509247 A CN111509247 A CN 111509247A CN 202010261124 A CN202010261124 A CN 202010261124A CN 111509247 A CN111509247 A CN 111509247A
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electrolyte
vanadium
exchange resin
composite electrode
battery
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CN111509247B (en
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刘涛
丁木清
张一敏
薛楠楠
刘红
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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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
    • H01M8/008—Disposal or recycling of fuel cells
    • 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
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    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention relates to a method for regenerating an electrolyte of a failure vanadium redox battery. The technical scheme is as follows: mixing the failure vanadium battery positive electrolyte with the failure vanadium battery negative electrolyte to obtain an electrolyte I; and adding a vanadium compound, a supporting electrolyte and deionized water, stirring, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II. Placing the anode composite electrode and the cathode composite electrode in sequence at the positive end and the negative end of the capacitive deionization device, and circularly pumping the electrolyte II into the capacitive deionization device under the condition that the direct-current voltage is 0.5-3V to obtain an electrolyte III; and (3) placing the electrolyte III in an electrolytic cell negative electrode chamber, adding a sulfuric acid solution with the same acidity as the electrolyte III into an electrolytic cell positive electrode chamber, and performing constant-current electrolysis under the condition that the current is 1-5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte. The method has the advantages of simple process, environmental friendliness, low cost and convenience for large-scale application, and the regenerated electrolyte has good stability and electrochemical performance and meets the normal use requirement.

Description

Method for regenerating electrolyte of failure vanadium battery
Technical Field
The invention belongs to the technical field of vanadium battery electrolyte. In particular to a method for regenerating the electrolyte of a failure vanadium redox battery.
Background
The vanadium redox battery has the advantages of long service life, low operation and maintenance cost, high reliability, strong safety, easiness in large-scale application and the like, and is widely applied. The vanadium battery electrolyte is an energy storage active substance of the vanadium battery as an important component of the vanadium battery, and the performance of the vanadium battery electrolyte directly determines the performance of the vanadium battery. With continuous charging and discharging of the vanadium battery, phenomena of vanadium ion migration, pentavalent vanadium ion precipitation in the positive electrolyte, divalent vanadium ion oxidation in the negative electrolyte and the like can be generated between the positive electrolyte and the negative electrolyte, so that the concentration and valence state of vanadium ions in the positive electrolyte and the negative electrolyte are unbalanced. In addition, in the operation process of the vanadium redox battery, impurity ions in the electrolyte can be accumulated continuously, so that the performance of the electrolyte can not meet the application requirement, and a new electrolyte needs to be replaced, thereby generating the failure vanadium redox battery electrolyte. Therefore, the research and development of the regeneration method of the electrolyte of the failed vanadium redox battery has very important significance for the industrialization and large-scale development of the vanadium redox battery.
At present, the regeneration method of the electrolyte of the failure vanadium battery is mainly to dilute the electrolyte, adjust the pH value of the electrolyte, precipitate vanadium, obtain solid vanadium compounds such as vanadium pentoxide or vanadyl sulfate and the like, and then dissolve the solid vanadium compounds to prepare the electrolyte. The process is complicated, the vanadium recovery rate is low, the electrolyte regeneration cost is high, and the environment is polluted by waste water and waste gas generated.
The patent technology of 'a regeneration method of a sulfuric acid system failure vanadium electrolyte' (CN109360997A) is to add a tetravalent vanadium electrolyte or a trivalent vanadium electrolyte and water into the failure vanadium battery electrolyte to obtain a regenerated electrolyte; the patent technology of 'a regeneration method of a failure vanadium battery electrolyte' (CN109065906A) is to add vanadium trichloride or vanadyl dichloride, hydrochloric acid and water into the failure electrolyte to obtain a regenerated electrolyte; the patent technology of 'a method for regenerating vanadium electrolyte by using negative electrolyte of a failed vanadium battery' (CN109461948A) comprises the steps of adding vanadium pentoxide and sulfuric acid into the negative electrolyte, carrying out solid-liquid separation after reaction, collecting liquid phase, and adding water for dilution to obtain regenerated electrolyte; the patent technology of 'method for regenerating vanadium electrolyte by using positive electrolyte of failed vanadium battery' (CN109148911A) adds vanadium dichloride, hydrochloric acid and water into the positive electrolyte to obtain regenerated electrolyte. Although the process has high vanadium recovery rate and simple operation, the problem of unbalanced valence state of vanadium ions in the electrolyte of the ineffective vanadium battery can only be solved.
In summary, the regeneration method of the current failure vanadium battery electrolyte generally adopts a mode of diluting and adjusting pH to precipitate vanadium to prepare a solid vanadium compound, and then dissolving the solid vanadium compound to prepare the electrolyte, so that the problems of complex process, high treatment cost, difficult vanadium recovery and utilization rate reaching 100%, environmental pollution caused by generated wastewater and the like exist; the method of adding the high-purity vanadium compound has the problem that the failure of the electrolyte caused by the influence of impurity ions cannot be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the regeneration method of the electrolyte of the failed vanadium battery, which has the advantages of simple process, high vanadium recovery and utilization rate, environmental friendliness, low treatment cost and convenience for large-scale application.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
mixing the positive electrolyte of the failed vanadium redox battery with the negative electrolyte of the failed vanadium redox battery to obtain an electrolyte I; adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte I, stirring for 0.5-12 h, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II; wherein:
the amount Mv of the vanadium species added to the vanadium compound
Mv＝CV2×V2－CVⅠ×V1(1)
The amount M of the substance of hydrogen ions added to the supporting electrolyteH2
MH2＝CH2×V2－CH1×V1(2)
In the formulae (1) and (2):
CVⅠthe concentration of vanadium ions in the electrolyte I is shown, mol/L;
CH1represents the hydrogen ion concentration in the electrolyte I, mol/L;
V1represents the volume of electrolyte i, L;
CV2represents the concentration of vanadium ions in the regenerated electrolyte, mol/L;
CH2represents the hydrogen ion concentration in the regenerated electrolyte, mol/L;
V2indicating the volume of regenerated electrolyte, L.
Step two, firstly, mixing a carbon material, anion exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-5: 0.05-0.5: 2-10, mixing the carbon material, the anion exchange resin, the binder and the organic solvent, and stirring for 2-6 hours to obtain a mixed solution I; and uniformly spraying or coating the mixed solution I on a graphite felt electrode, and drying at 40-75 ℃ to obtain the anode composite electrode.
The anion exchange resin is more than one of primary amino anion exchange resin, secondary amino anion exchange resin and tertiary amino anion exchange resin; the particle size of the anion exchange resin is less than 74 mu m and accounts for 60-85 wt%.
Mixing a carbon material, a cation exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-5: 0.05-0.5: 2-10, mixing the carbon material, the cation exchange resin, the binder and the organic solvent, and stirring for 2-6 hours to obtain a mixed solution II; and uniformly spraying or coating the mixed solution II on a graphite felt electrode, and drying at 40-75 ℃ to obtain the cathode composite electrode.
The cation exchange resin is more than one of sulfonic cation exchange resin, carboxyl cation exchange resin, thiourea cation exchange resin and imine diacetic cation exchange resin; the particle size of the cation exchange resin is less than 74 mu m and accounts for 60-85 wt%.
And fourthly, sequentially placing the anode composite electrode and the cathode composite electrode at the positive end and the negative end of the capacitive deionization device, switching on a direct-current power supply, setting the voltage to be 0.5-3V, and circularly pumping the electrolyte II into the capacitive deionization device, wherein the flow of the electrolyte II passing through the composite electrode per square meter is 5-40L/min, and the circulation time is 0.5-6 h, so that the electrolyte III is obtained.
The composite electrode is the anode composite electrode and the cathode composite electrode.
Putting the electrolyte III in a negative electrode chamber of an electrolytic cell, and adding a sulfuric acid solution into a positive electrode chamber of the electrolytic cell, wherein the acidity of the sulfuric acid solution is the same as that of the electrolyte III; and then switching on a power supply, and carrying out constant-current electrolysis under the condition that the current is 1-5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte.
The supporting electrolyte is more than one of sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, taurine and sulfamic acid.
The vanadium compound is more than one of vanadium pentoxide, vanadium trioxide and vanadium dioxide; the purity of the vanadium compound is more than or equal to 99.5 percent.
The carbon material in the second step and the third step is more than one of activated carbon, graphene, carbon nano tubes and acetylene black; the carbon material has a particle size of less than 74 μm and accounts for 60-85 wt%.
The binder in the second step and the third step is more than one of polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl alcohol.
The organic solvent in the second step and the third step is one of ethanol, acetone, dimethylacetamide and dimethylformamide.
Compared with the prior art, the method has the following positive effects:
1. the method comprises the steps of adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte of the failed vanadium battery, adjusting the concentration and the acidity of vanadium ions, then preparing a cathode composite electrode by using cation exchange resin, preparing an anode composite electrode by using anion exchange resin, adsorbing and removing impurity ions in the electrolyte of the failed vanadium battery, finally electrolyzing, and adjusting the valence state of the vanadium ions of the regenerated electrolyte to be 3.5, so that the regenerated electrolyte is obtained, wherein the vanadium concentration of the regenerated electrolyte is 1-3 mol/L, the hydrogen ion concentration is 4-12 mol/L, the concentration and the acidity of the vanadium ions meet the requirements of normal use, the content of the impurity ions in the regenerated electrolyte is lower than 100 mg/L, and the valence state of the vanadium ions is stable 3.5, so that the regenerated electrolyte has good electrochemical performance and extremely high stability.
2. The method for regenerating the electrolyte of the failed vanadium battery not only avoids the problem that the electrolyte of the failed vanadium battery is firstly precipitated to prepare the solid vanadium compound, but also avoids the existing complex process for preparing the electrolyte by dissolving the solid vanadium compound. The capacitor deionization device and the electrolysis process are both low voltage and low current, the treatment energy consumption is low, no chemical agent is required to be added, and the treatment cost is low. The method firstly adds the vanadium compound, the supporting electrolyte and the deionized water into the electrolyte (namely the electrolyte I) of the failure vanadium battery to adjust the concentration and the acidity of the vanadium, then removes impurity ions by adopting a capacitance deionization method, and finally adjusts the valence state of the vanadium by adopting an electrolysis method without complex processes and equipment for adjusting the concentration, the acidity, the valence state of the vanadium and removing impurities.
According to the invention, electrochemical tests show that the electrolyte of the failure vanadium battery has poor electrochemical reversibility and severe oxygen and hydrogen evolution side reactions; according to the invention, electrochemical tests show that the regenerated electrolyte prepared from the spent vanadium battery electrolyte obviously improves the electrochemical reversibility of the regenerated electrolyte, obviously reduces oxygen evolution and hydrogen evolution side reactions, and obviously improves the electrochemical performance. The regenerated electrolyte prepared by the invention is loaded into a vanadium battery charging and discharging test system, and is subjected to charging and discharging circulation for 500 times: the coulomb efficiency is 90-95%; the energy efficiency is 70-76%.
Therefore, the method has the characteristics of simple process, high vanadium recovery and utilization rate, environmental friendliness, low treatment cost and convenience for large-scale application, and the concentration, valence state and acidity of the vanadium ions in the regenerated electrolyte prepared by the method not only meet the requirements of normal use, but also have good stability and electrochemical performance.
Drawings
FIG. 1 is a cyclic voltammogram of a spent vanadium battery electrolyte employed in the present invention;
figure 2 is a cyclic voltammogram of a regenerated electrolyte prepared with the spent vanadium battery electrolyte shown in figure 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting its scope.
In order to avoid repetition, the materials related to this specific embodiment are described in a unified manner, which is not described in the embodiments again:
the anion exchange resin is more than one of primary amine anion exchange resin, secondary amine anion exchange resin and tertiary amine anion exchange resin; the particle size of the anion exchange resin is less than 74 mu m and accounts for 60-85 wt%.
The cation exchange resin is more than one of sulfonic cation exchange resin, carboxyl cation exchange resin, thiourea cation exchange resin and imine diacetic cation exchange resin; the particle size of the cation exchange resin is less than 74 mu m and accounts for 60-85 wt%.
The supporting electrolyte is more than one of sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, taurine and sulfamic acid.
The vanadium compound is more than one of vanadium pentoxide, vanadium trioxide and vanadium dioxide; the purity of the vanadium compound is more than or equal to 99.5 percent.
The carbon material in the second step and the third step is more than one of activated carbon, graphene, carbon nano tubes and acetylene black; the carbon material has a particle size of less than 74 μm and accounts for 60-85 wt%.
The binder in the second step and the third step is more than one of polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl alcohol.
The organic solvent in the second step and the third step is one of ethanol, acetone, dimethylacetamide and dimethylformamide.
Example 1
A method for regenerating an electrolyte of a failed vanadium redox battery. The method of the embodiment comprises the following specific steps:
step one, mixing the positive electrolyte of the failure vanadium redox battery with the negative electrolyte of the failure vanadium redox battery to obtain an electrolyte I, wherein the electrolyte I: concentration of vanadium ion CVⅠ0.7 to 0.9 mol/L, hydrogen ion concentration CH12-3 mol/L, volume V1Adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte I, stirring for 0.5-5 h, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II;
the amount Mv of the vanadium species added to the vanadium compound
Mv＝CV2×V2－CVⅠ×V1(1)
The amount M of the substance of hydrogen ions added to the supporting electrolyteH2
MH2＝CH2×V2－CH1×V1(2)
In the formulae (1) and (2):
CVⅠindicates the concentration of vanadium ions in the electrolyte I, CVⅠ＝0.7～0.9mol/L；
CH1Represents the hydrogen ion concentration, C, in the electrolyte IH1＝2～3mol/L；
V1Represents the volume of electrolyte i, 10L;
CV2indicates the concentration of vanadium ions, C, in the regenerated electrolyteV2＝1～1.65mol/L；
CH2Represents the hydrogen ion concentration, C, in the regenerated electrolyteH2＝4～7mol/L；
V2The volume of regenerated electrolyte, 10L, is indicated.
Represented by the formula (1) (2):
the amount Mv of the vanadium ion added to the vanadium compound is 1-9.5 mol;
adding the supporting electrolyteAmount of hydrogen ion species MH2＝10～50mol。
Step two, firstly, mixing a carbon material, anion exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-2.5: 0.05-0.25: 2-6, mixing the carbon material, the anion exchange resin, the binder and the organic solvent, and stirring for 2-4 hours to obtain a mixed solution I; and uniformly spraying or coating the mixed solution I on a graphite felt electrode, and drying at 40-65 ℃ to obtain the anode composite electrode.
Mixing a carbon material, a cation exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-2.5: 0.05-0.25: 2-6, mixing the carbon material, the cation exchange resin, the binder and the organic solvent, and stirring for 2-4 hours to obtain a mixed solution II; and uniformly spraying or coating the mixed solution II on a graphite felt electrode, and drying at 40-65 ℃ to obtain the cathode composite electrode.
And fourthly, sequentially placing the anode composite electrode and the cathode composite electrode at the positive end and the negative end of the capacitive deionization device, switching on a direct-current power supply, setting the voltage to be 0.5-2V, and circularly pumping the electrolyte II into the capacitive deionization device, wherein the flow of the electrolyte II passing through the composite electrode per square meter is 5-20L/min, and the circulation time is 0.5-3.5 h, so that the electrolyte III is obtained.
The composite electrode is the anode composite electrode and the cathode composite electrode.
Putting the electrolyte III in a negative electrode chamber of an electrolytic cell, and adding a sulfuric acid solution into a positive electrode chamber of the electrolytic cell, wherein the acidity of the sulfuric acid solution is the same as that of the electrolyte III; and then switching on a power supply, and carrying out constant-current electrolysis under the condition that the current is 1-3.5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte.
The regenerated electrolyte prepared from the electrolyte of the failed vanadium redox battery in the embodiment: concentration of vanadium CV21-1.65 mol/L, hydrogen ion concentration CH24-7 mol/L, the valence of the vanadium ion is 3.5, and the concentration of the impurity ions in the electrolyte is 75-90 mgL, the regenerated electrolyte is filled into a vanadium battery charging and discharging test system, and charging and discharging circulation is carried out for 500 times, wherein the coulombic efficiency is 90-94%, and the energy efficiency is 72-75%.
Example 2
A method for regenerating an electrolyte of a failed vanadium redox battery. The method of the embodiment comprises the following specific steps:
step one, mixing the positive electrolyte of the failure vanadium redox battery with the negative electrolyte of the failure vanadium redox battery to obtain an electrolyte I, wherein the electrolyte I: concentration of vanadium ion CVⅠ0.8 to 1.0 mol/L, hydrogen ion concentration CH13-4 mol/L, volume V1Adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte I, stirring for 3-8 h, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II;
the amount Mv of the vanadium species added to the vanadium compound
Mv＝CV2×V2－CVⅠ×V1(1)
The amount M of the substance of hydrogen ions added to the supporting electrolyteH2
MH2＝CH2×V2－CH1×V1(2)
In the formulae (1) and (2):
CVⅠindicates the concentration of vanadium ions in the electrolyte I, CVⅠ＝0.8～1.0mol/L；
CH1Represents the hydrogen ion concentration, C, in the electrolyte IH1＝3～4mol/L；
V1Represents the volume of electrolyte i, 20L;
CV2indicates the concentration of vanadium ions, C, in the regenerated electrolyteV2＝1.6～2.3mol/L；
CH2Represents the hydrogen ion concentration, C, in the regenerated electrolyteH2＝5～9mol/L；
V2Indicating the volume of regenerated electrolyte, 20L.
Represented by the formula (1) (2):
the amount Mv of the vanadium ion added to the vanadium compound is 12-30 mol;
the amount M of the substance of hydrogen ions added to the supporting electrolyteH2＝20～120mol。
Step two, firstly, mixing a carbon material, anion exchange resin, a binder and an organic solvent according to the mass ratio of 1: 2-4.5: 0.2-0.35: 6-8, mixing the carbon material, the anion exchange resin, the binder and the organic solvent, and stirring for 3-5 hours to obtain a mixed solution I; and uniformly spraying or coating the mixed solution I on a graphite felt electrode, and drying at 50-70 ℃ to obtain the anode composite electrode.
Mixing a carbon material, a cation exchange resin, a binder and an organic solvent according to the mass ratio of 1: 2-4.5: 0.2-0.35: 5-9, mixing the carbon material, the cation exchange resin, the binder and the organic solvent, and stirring for 3-5 hours to obtain a mixed solution II; and uniformly spraying or coating the mixed solution II on a graphite felt electrode, and drying at 50-70 ℃ to obtain the cathode composite electrode.
And fourthly, sequentially placing the anode composite electrode and the cathode composite electrode at the positive end and the negative end of the capacitive deionization device, switching on a direct-current power supply, setting the voltage to be 1.5-2.5V, and circularly pumping the electrolyte II into the capacitive deionization device, wherein the flow of the electrolyte II passing through the composite electrode per square meter is 15-30L/min, and the circulation time is 3-5 h, so that the electrolyte III is obtained.
The composite electrode is the anode composite electrode and the cathode composite electrode.
Putting the electrolyte III in a negative electrode chamber of an electrolytic cell, and adding a sulfuric acid solution into a positive electrode chamber of the electrolytic cell, wherein the acidity of the sulfuric acid solution is the same as that of the electrolyte III; and then switching on a power supply, and carrying out constant-current electrolysis under the condition that the current is 3-4.5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte.
The regenerated electrolyte prepared from the electrolyte of the failed vanadium redox battery in the embodiment: concentration of vanadium CV21.6-2.3 mol/L, hydrogen ion concentration CH25-9 mol/L, vanadium ion valenceThe state is 3.5-valent, the concentration of impurity ions in the electrolyte is 80-100 mg/L, the regenerated electrolyte is filled into a vanadium cell charging and discharging test system, and charging and discharging cycles are carried out for 500 times, wherein the coulombic efficiency is 90-93%, and the energy efficiency is 70-74%.
Example 3
A method for regenerating an electrolyte of a failed vanadium redox battery. The method of the embodiment comprises the following specific steps:
step one, mixing the positive electrolyte of the failure vanadium redox battery with the negative electrolyte of the failure vanadium redox battery to obtain an electrolyte I, wherein the electrolyte I: concentration of vanadium ion CVⅠ1.2 to 1.5 mol/L, hydrogen ion concentration CH14-6 mol/L, volume V1Adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte I, stirring for 7-12 h, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II;
the amount Mv of the vanadium species added to the vanadium compound
Mv＝CV2×V2－CVⅠ×V1(1)
The amount M of the substance of hydrogen ions added to the supporting electrolyteH2
MH2＝CH2×V2－CH1×V1(2)
In the formulae (1) and (2):
CVⅠindicates the concentration of vanadium ions in the electrolyte I, CVⅠ＝1.2～1.5mol/L；
CH1Represents the hydrogen ion concentration, C, in the electrolyte IH1＝4～6mol/L；
V1Represents the volume of electrolyte i, 20L;
CV2indicates the concentration of vanadium ions, C, in the regenerated electrolyteV2＝1.8～3mol/L；
CH2Represents the hydrogen ion concentration, C, in the regenerated electrolyteH2＝8～12mol/L；
V2Indicating the volume of regenerated electrolyte, 20L.
Represented by the formula (1) (2):
the amount Mv of the vanadium ion substance added to the vanadium compound is 6-36 mol;
the amount M of the substance of hydrogen ions added to the supporting electrolyteH2＝40～160mol。
Step two, firstly, mixing a carbon material, anion exchange resin, a binder and an organic solvent according to the mass ratio of 1: 4-5: 0.3-0.5: 8-10, mixing the carbon material, the anion exchange resin, the binder and the organic solvent, and stirring for 4-6 hours to obtain a mixed solution I; and uniformly spraying or coating the mixed solution I on a graphite felt electrode, and drying at the temperature of 60-75 ℃ to obtain the anode composite electrode.
Mixing a carbon material, a cation exchange resin, a binder and an organic solvent according to the mass ratio of 1: 4-5: 0.3-0.5: 8-10, and stirring for 4-6 hours to obtain a mixed solution II; and uniformly spraying or coating the mixed solution II on a graphite felt electrode, and drying at the temperature of 60-75 ℃ to obtain the cathode composite electrode.
And fourthly, sequentially placing the anode composite electrode and the cathode composite electrode at the positive end and the negative end of the capacitive deionization device, switching on a direct-current power supply, setting the voltage to be 2-3V, and circularly pumping the electrolyte II into the capacitive deionization device, wherein the flow of the electrolyte II passing through the composite electrode per square meter is 25-40L/min, and the circulation time is 4-6 h, so that the electrolyte III is obtained.
The composite electrode is the anode composite electrode and the cathode composite electrode.
Putting the electrolyte III in a negative electrode chamber of an electrolytic cell, and adding a sulfuric acid solution into a positive electrode chamber of the electrolytic cell, wherein the acidity of the sulfuric acid solution is the same as that of the electrolyte III; and then switching on a power supply, and carrying out constant-current electrolysis under the condition that the current is 3.5-5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte.
The regenerated electrolyte prepared from the electrolyte of the failed vanadium redox battery in the embodiment: concentration of vanadium CV21.8 to 3 mol/L, hydrogen dissociationSub concentration CH2The vanadium ion battery regeneration method comprises the following steps of (1) loading the regenerated electrolyte into a vanadium battery charging and discharging test system, wherein the vanadium ion valence is 8-12 mol/L, the vanadium ion valence is 3.5, the impurity ion concentration in the electrolyte is 55-70 mg/L, the charging and discharging cycle is carried out for 500 times, the coulomb efficiency is 92-95%, and the energy efficiency is 73-76%.
Compared with the prior art, the specific implementation mode has the following positive effects:
1. the method comprises the steps of adding a vanadium compound, a supporting electrolyte and deionized water into a spent vanadium battery electrolyte, adjusting the concentration and the acidity of vanadium ions, then preparing a cathode composite electrode by using cation exchange resin, preparing an anode composite electrode by using anion exchange resin, adsorbing and removing impurity ions in the spent vanadium battery electrolyte, finally electrolyzing, and adjusting the valence state of the vanadium ions of a regenerated electrolyte to be 3.5, so as to obtain the regenerated electrolyte, wherein the vanadium concentration of the regenerated electrolyte is 1-3 mol/L, the hydrogen ion concentration is 4-12 mol/L, the concentration and the acidity of the vanadium ions meet the requirements of normal use, the content of the impurity ions in the regenerated electrolyte is lower than 100 mg/L, and the valence state of the vanadium ions is stable and is 3.5, so that the regenerated electrolyte has good electrochemical performance and extremely high stability.
2. The method for regenerating the electrolyte of the failed vanadium battery in the embodiment not only avoids the problem that the electrolyte of the failed vanadium battery is firstly precipitated to prepare the solid vanadium compound, but also avoids the existing complex process for preparing the electrolyte by dissolving the solid vanadium compound. The capacitor deionization device and the electrolysis process are both low voltage and low current, the treatment energy consumption is low, no chemical agent is required to be added, and the treatment cost is low. In the specific embodiment, firstly, a vanadium compound, a supporting electrolyte and deionized water are added into the electrolyte (namely the electrolyte I) of the failed vanadium battery shown in FIG. 1 to adjust the concentration and the acidity of vanadium, then impurity ions are removed by adopting a capacitive deionization method, and finally, the valence state of vanadium is adjusted by adopting an electrolysis method without complex processes and equipment for adjusting the concentration, the acidity and the valence state of vanadium and removing impurities.
Fig. 1 shows a cyclic voltammetry curve of the spent vanadium battery electrolyte used in example 1, and as can be seen from fig. 1, the spent vanadium battery electrolyte has poor electrochemical reversibility and severe oxygen and hydrogen evolution side reactions; the regenerated electrolyte prepared by the embodiment is shown in fig. 2 after electrochemical tests, fig. 2 is a cyclic voltammetry curve diagram of the regenerated electrolyte prepared by the spent vanadium battery electrolyte shown in fig. 1, and as can be seen from fig. 2, the electrochemical reversibility of the regenerated electrolyte is remarkably improved, the oxygen evolution and hydrogen evolution side reactions are remarkably reduced, and the electrochemical performance is remarkably improved. And (3) filling the regenerated electrolyte into a vanadium battery charging and discharging test system, and performing charging and discharging circulation for 500 times: the coulomb efficiency is 90-95%; the energy efficiency is 70-76%.
Therefore, the specific implementation mode has the characteristics of simple process, high vanadium recovery utilization rate, environmental friendliness, low treatment cost and convenience for large-scale application, and the concentration, valence and acidity of the vanadium ions in the regenerated electrolyte prepared by the method not only meet the requirements of normal use, but also have good stability and electrochemical performance.

Claims (6)

1. A method for regenerating an electrolyte of a failed vanadium battery is characterized by comprising the following specific steps:
mixing the positive electrolyte of the failed vanadium redox battery with the negative electrolyte of the failed vanadium redox battery to obtain an electrolyte I; adding a vanadium compound, a supporting electrolyte and deionized water into the electrolyte I, stirring for 0.5-12 h, carrying out solid-liquid separation, and collecting a liquid phase to obtain an electrolyte II; wherein:
the amount Mv of the vanadium species added to the vanadium compound
Mv＝CV2×V2－CVⅠ×V1(1)
The amount M of the substance of hydrogen ions added to the supporting electrolyteH2
MH2＝CH2×V2－CH1×V1(2)
In the formulae (1) and (2):
CVⅠthe concentration of vanadium ions in the electrolyte I is shown, mol/L;
CH1represents the hydrogen ion concentration in the electrolyte I, mol/L;
V1represents the volume of electrolyte i, L;
CV2represents the concentration of vanadium ions in the regenerated electrolyte, mol/L;
CH2represents the hydrogen ion concentration in the regenerated electrolyte, mol/L;
V2indicating the volume of regenerated electrolyte, L;
step two, firstly, mixing a carbon material, anion exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-5: 0.05-0.5: 2-10, mixing the carbon material, the anion exchange resin, the binder and the organic solvent, and stirring for 2-6 hours to obtain a mixed solution I; uniformly spraying or coating the mixed solution I on a graphite felt electrode, and drying at 40-75 ℃ to obtain an anode composite electrode;
the anion exchange resin is more than one of primary amino anion exchange resin, secondary amino anion exchange resin and tertiary amino anion exchange resin; the particle size of the anion exchange resin is less than 74 mu m and accounts for 60-85 wt%;
mixing a carbon material, a cation exchange resin, a binder and an organic solvent according to the mass ratio of 1: 0.5-5: 0.05-0.5: 2-10, mixing the carbon material, the cation exchange resin, the binder and the organic solvent, and stirring for 2-6 hours to obtain a mixed solution II; uniformly spraying or coating the mixed solution II on a graphite felt electrode, and drying at 40-75 ℃ to obtain a cathode composite electrode;
the cation exchange resin is more than one of sulfonic cation exchange resin, carboxyl cation exchange resin, thiourea cation exchange resin and imine diacetic cation exchange resin; the particle size of the cation exchange resin is less than 74 mu m and accounts for 60-85 wt%;
step four, sequentially placing the anode composite electrode and the cathode composite electrode at the positive end and the negative end of the capacitive deionization device, switching on a direct-current power supply, setting the voltage to be 0.5-3V, circularly pumping the electrolyte II into the capacitive deionization device, wherein the flow of the electrolyte II passing through the composite electrode per square meter is 5-40L/min, and the circulation time is 0.5-6 h, so as to obtain an electrolyte III;
the composite electrode is the anode composite electrode and the cathode composite electrode;
putting the electrolyte III in a negative electrode chamber of an electrolytic cell, and adding a sulfuric acid solution into a positive electrode chamber of the electrolytic cell, wherein the acidity of the sulfuric acid solution is the same as that of the electrolyte III; and then switching on a power supply, and carrying out constant-current electrolysis under the condition that the current is 1-5A until the valence state of the electrolyte is 3.5, thus obtaining the regenerated electrolyte.
2. The method of regenerating a spent vanadium battery electrolyte according to claim 1, wherein the supporting electrolyte is one or more of sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, taurine and sulfamic acid.
3. The method of claim 1, wherein the vanadium compound is one or more of vanadium pentoxide, vanadium trioxide and vanadium dioxide; the purity of the vanadium compound is more than or equal to 99.5 percent.
4. The method for regenerating the spent vanadium battery electrolyte according to claim 1, wherein the carbon material in the second step and the third step is one or more of activated carbon, graphene, carbon nanotubes and acetylene black; the carbon material has a particle size of less than 74 μm and accounts for 60-85 wt%.
5. The method for regenerating the electrolyte of the failed vanadium redox battery according to claim 1, wherein the binder in the second step and the third step is one or more of polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl alcohol.
6. The method for regenerating the electrolyte of the failed vanadium redox battery according to claim 1, wherein the organic solvent in the second step and the third step is one of ethanol, acetone, dimethylacetamide and dimethylformamide.
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