CN110808396A - Vanadium battery positive electrode electrolyte for increasing pentavalent vanadium ion solubility - Google Patents
Vanadium battery positive electrode electrolyte for increasing pentavalent vanadium ion solubility Download PDFInfo
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- CN110808396A CN110808396A CN201910981541.XA CN201910981541A CN110808396A CN 110808396 A CN110808396 A CN 110808396A CN 201910981541 A CN201910981541 A CN 201910981541A CN 110808396 A CN110808396 A CN 110808396A
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of all-vanadium redox flow batteries, and discloses a vanadium battery positive electrolyte for increasing the solubility of pentavalent vanadium ions, which comprises the following raw materials in parts by weight: from 1.5 to 2mol/L of VOSO4And 3 to 4mol/L of H2SO4The mixed solution comprises 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol. The invention solves the technical problem that the existing positive electrode electrolyte of the all-vanadium redox flow battery has low solubility of high-concentration active substance pentavalent vanadium ions in sulfuric acid solution.
Description
Technical Field
The invention relates to the technical field of all-vanadium redox flow batteries, in particular to a vanadium battery positive electrode electrolyte for increasing the solubility of pentavalent vanadium ions.
Background
The all-vanadium redox flow battery has the advantages of adjustable energy storage capacity and power, large-current lossless deep discharge, long service life, simple operation and maintenance, environmental protection and the like, is concerned, is greatly developed in recent years, and is gradually going to be practical.
The vanadium battery anode initial solution completes anode reaction under certain acidic condition, and pentavalent vanadium ion solution is obtained after charging. Because the solubility of pentavalent vanadium ions is low, red polyvanadate precipitates can be separated out when the high-concentration positive electrode solution is close to a full-charge state, and the surface of a porous electrode can be blocked, so that the battery cannot be used.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides vanadium battery positive electrolyte for increasing the solubility of pentavalent vanadium ions, which is used for solving the technical problem that the high-concentration active substance pentavalent vanadium ions in a sulfuric acid solution have low solubility in the existing all-vanadium redox flow battery positive electrolyte.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
the vanadium battery positive electrode electrolyte for increasing the solubility of pentavalent vanadium ions comprises the following raw materials in parts by weight: from 1.5 to 2mol/L of VOSO4And 3 to 4mol/L of H2SO4The mixed solution comprises a mixed cosolvent consisting of 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: preparing 1.5-2 mol/L VOSO4And 3 to 4mol/L of H2SO4A mixed solution of the components;
step two: adding a mixed cosolvent consisting of 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol into the prepared mixed solution, fully dissolving, and transferring to a cathode chamber of an electrolytic cell; equal volume of 3-4 mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, and preparing tetravalent vanadium ions (V (IV)) electrolyte in a cathode chamber of an electrolytic cell;
step four: and (3) charging the prepared tetravalent vanadium ion { V (IV) } electrolyte at a constant voltage under the voltage of 1.7V, and obtaining a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode, namely preparing the positive electrode electrolyte of the vanadium battery.
Further, the vanadium battery positive electrode electrolyte comprises: from 2mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 10g of sodium sulfate and 15g of glycerol.
Further, the vanadium battery positive electrode electrolyte comprises: from 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 12g of sodium sulfate and 12g of glycerol.
Further, the vanadium battery positive electrode electrolyte comprises: from 1.5mol/L VOSO4+4mol/L of H2SO41L of mixed solution, a mixture of 14g of sodium sulfate and 8g of glycerolA cosolvent.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the invention is prepared by adding 1.5-2 mol/L VOSO4And 3 to 4mol/L of H2SO4Adding a mixed cosolvent consisting of 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol into the mixed solution, and preparing a vanadium battery positive electrolyte by adopting an electrolytic synthesis method, wherein the solubility of pentavalent vanadium ions V (V) in the vanadium battery positive electrolyte is 91-94%;
compared with 81% of the solubility of the pentavalent vanadium ion V (V) in the positive electrolyte of the vanadium battery prepared in the comparative example, the technical effect of remarkably improving the solubility of the pentavalent vanadium ion in a sulfuric acid solution is achieved;
therefore, the technical problem that the solubility of high-concentration active substance pentavalent vanadium ions in a sulfuric acid solution is low in the existing all-vanadium redox flow battery anode electrolyte is solved.
Detailed Description
The first embodiment is as follows:
the vanadium battery positive electrolyte comprises the following raw materials: from 2mol/L VOSO4+3mol/L of H2SO41L of mixed solution, and mixed cosolvent consisting of 15g of sodium sulfate and 10g of glycerol;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: will V2O5Heating and activating in concentrated sulfuric acid until the solution is a red-blood viscous solid, cooling, and diluting with high-purity deionized water to constant volume to obtain 2mol/L VOSO4+3mol/L of H2SO41L of mixed solution;
step two: adding a mixed cosolvent consisting of 15g of sodium sulfate and 10g of glycerol into the mixed solution in the step one, fully dissolving, and transferring to a cathode chamber of an electrolytic cell;
then, an equal volume of 3mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, wherein the stirring speed is 300r/min, and the electrolysis reaches the end point, thus preparing tetravalent vanadium ion { V (IV) } electrolyte;
step four: and (3) placing the V (IV) electrolyte prepared in the step three in a dynamic battery liquid storage tank, keeping the volume and concentration of the positive and negative electrolytes the same, and charging at a constant voltage of 1.7V to obtain a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode and a dark green trivalent vanadium ion { V (III) } electrolyte at the negative electrode, wherein the V (V) electrolyte is the vanadium battery positive electrolyte.
Example two:
the vanadium battery positive electrolyte comprises the following raw materials: from 2mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and mixed cosolvent consisting of 10g of sodium sulfate and 15g of glycerol;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: will V2O5Heating and activating in concentrated sulfuric acid until the solution is a red-blood viscous solid, cooling, and diluting with high-purity deionized water to constant volume to obtain 2mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution;
step two: adding a mixed cosolvent consisting of 10g of sodium sulfate and 15g of glycerol into the mixed solution in the step one, fully dissolving, and transferring to a cathode chamber of an electrolytic cell;
thereafter, an equal volume of 3.5mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, wherein the stirring speed is 200r/min, and the electrolysis reaches the end point, thus preparing tetravalent vanadium ion { V (IV) } electrolyte;
step four: and (3) placing the V (IV) electrolyte prepared in the step three in a dynamic battery liquid storage tank, keeping the volume and concentration of the positive and negative electrolytes the same, and charging at a constant voltage of 1.7V to obtain a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode and a dark green trivalent vanadium ion { V (III) } electrolyte at the negative electrode, wherein the V (V) electrolyte is the vanadium battery positive electrolyte.
Example three:
the vanadium battery positive electrolyte comprises the following raw materials: from 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 12g of sodium sulfate and 12g of glycerol;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: will V2O5Heating and activating in concentrated sulfuric acid until the solution is a red-blood viscous solid, cooling, and diluting with high-purity deionized water to constant volume to obtain 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution;
step two: adding a mixed cosolvent consisting of 12g of sodium sulfate and 12g of glycerol into the mixed solution in the step one, fully dissolving, and transferring to a cathode chamber of an electrolytic cell;
thereafter, an equal volume of 3.5mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, wherein the stirring speed is 300r/min, and the electrolysis reaches the end point, thus preparing tetravalent vanadium ion { V (IV) } electrolyte;
step four: and (3) placing the V (IV) electrolyte prepared in the step three in a dynamic battery liquid storage tank, keeping the volume and concentration of the positive and negative electrolytes the same, and charging at a constant voltage of 1.7V to obtain a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode and a dark green trivalent vanadium ion { V (III) } electrolyte at the negative electrode, wherein the V (V) electrolyte is the vanadium battery positive electrolyte.
Example four:
the vanadium battery positive electrolyte comprises the following raw materials: from 1.5mol/L VOSO4+4mol/L of H2SO41L of mixed solution, and mixed cosolvent consisting of 14g of sodium sulfate and 8g of glycerol;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: will V2O5Heating and activating in concentrated sulfuric acid until the solution is a red-blood viscous solid, cooling, and diluting with high-purity deionized water to constant volume to obtain 1.5mol/L VOSO4+4mol/L of H2SO41L of mixed solution;
step two: adding a mixed cosolvent consisting of 14g of sodium sulfate and 8g of glycerol into the mixed solution in the step one, fully dissolving, and transferring to a cathode chamber of an electrolytic cell;
thereafter, an equal volume of 4mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, wherein the stirring speed is 200r/min, and the electrolysis reaches the end point, thus preparing tetravalent vanadium ion { V (IV) } electrolyte;
step four: and (3) placing the V (IV) electrolyte prepared in the step three in a dynamic battery liquid storage tank, keeping the volume and concentration of the positive and negative electrolytes the same, and charging at a constant voltage of 1.7V to obtain a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode and a dark green trivalent vanadium ion { V (III) } electrolyte at the negative electrode, wherein the V (V) electrolyte is the vanadium battery positive electrolyte.
Comparative example:
the vanadium battery positive electrolyte comprises the following raw materials: from 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution;
the preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: will V2O5Heating and activating in concentrated sulfuric acid until the solution is a red-blood viscous solid, cooling, and diluting with high-purity deionized water to constant volume to obtain 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution;
step two: transferring the mixed solution in the step one to a cathode chamber of an electrolytic cell;
thereafter, an equal volume of 3.5mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, wherein the stirring speed is 300r/min, and the electrolysis reaches the end point, thus preparing tetravalent vanadium ion { V (IV) } electrolyte;
step four: and (3) placing the V (IV) electrolyte prepared in the step three in a dynamic battery liquid storage tank, keeping the volume and concentration of the positive and negative electrolytes the same, and charging at a constant voltage of 1.7V to obtain a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode and a dark green trivalent vanadium ion { V (III) } electrolyte at the negative electrode, wherein the V (V) electrolyte is the vanadium battery positive electrolyte.
And (3) performance testing:
the pentavalent vanadium ion V (V) is determined by the following method:
weighing 1.000g of sample, placing the sample in a square porcelain boat, then placing the square porcelain boat in a high-temperature furnace, slightly opening a furnace door, heating to 550 ℃, and keeping the temperature for 2 hours; after removal and cooling, the sample was transferred to a 50mL Teflon beaker and 10mL of H was added2SO4(1+1) and 5mL of HF, heated until the sample completely decomposed, removed and cooled and the solution transferred to a container containing 50mL of H2SO4(1+1), 20mL of saturated H3BO3And 5mL of H3PO4(1+1) in a 400mL beaker, diluted to 200mL with water and treated with Fe2+Standard solution titration v (v);
the pentavalent vanadium ion (v) concentrations of the pentavalent vanadium ion { v (v) } electrolytes prepared in the above examples and comparative examples were measured by the above-described method, and the results of the measurements are shown in table 1 below.
TABLE 1
Claims (4)
1. The vanadium battery positive electrode electrolyte for increasing the solubility of pentavalent vanadium ions is characterized by comprising the following raw materials in parts by weight: from 1.5 to 2mol/L of VOSO4And 3 to 4mol/L of H2SO4The mixed solution comprises 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol as mixed cosolvent；
The preparation method of the vanadium battery anode electrolyte comprises the following steps:
the method comprises the following steps: preparing 1.5-2 mol/L VOSO4And 3 to 4mol/L of H2SO4A mixed solution of the components;
step two: adding a mixed cosolvent consisting of 0.070-0.106 mol/L sodium sulfate and 0.086-0.163 mol/L glycerol into the prepared mixed solution, fully dissolving, and transferring to a cathode chamber of an electrolytic cell; equal volume of 3-4 mol/L H2SO4Adding into the anode chamber of the electrolytic cell;
step three: carrying out constant current electrolysis under the current of 6A, and preparing tetravalent vanadium ions (V (IV)) electrolyte in a cathode chamber of an electrolytic cell;
step four: and (3) charging the prepared tetravalent vanadium ion { V (IV) } electrolyte at a constant voltage under the voltage of 1.7V, and obtaining a red-blood pentavalent vanadium ion { V (V) } electrolyte at the positive electrode, namely preparing the positive electrode electrolyte of the vanadium battery.
2. The vanadium battery positive electrolyte according to claim 1, comprising: from 2mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 10g of sodium sulfate and 15g of glycerol.
3. The vanadium battery positive electrolyte according to claim 2, comprising: from 1.5mol/L VOSO4+3.5mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 12g of sodium sulfate and 12g of glycerol.
4. The vanadium battery positive electrolyte according to claim 3, comprising: from 1.5mol/L VOSO4+4mol/L of H2SO41L of mixed solution, and a mixed cosolvent consisting of 14g of sodium sulfate and 8g of glycerol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113764708A (en) * | 2021-09-03 | 2021-12-07 | 北京阳光鸿志电气工程技术有限公司 | Solid vanadium battery and preparation method thereof |
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| CN113764708A (en) * | 2021-09-03 | 2021-12-07 | 北京阳光鸿志电气工程技术有限公司 | Solid vanadium battery and preparation method thereof |
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Application publication date: 20200218 |