CN106972186B - Preparation method of composite membrane with catalytic function on positive electrode and negative electrode for all-vanadium redox flow battery - Google Patents
Preparation method of composite membrane with catalytic function on positive electrode and negative electrode for all-vanadium redox flow battery Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 150000003460 sulfonic acids Chemical class 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ABKDZANKXKCXKG-UHFFFAOYSA-B P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] ABKDZANKXKCXKG-UHFFFAOYSA-B 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003014 ion exchange membrane Substances 0.000 abstract description 6
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 238000010345 tape casting Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 description 8
- 239000002346 layers by function Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to the field of ion exchange membranes for all-vanadium redox flow batteries (VRB), in particular to a preparation method of a composite membrane with catalytic functions on positive and negative electrodes for all-vanadium redox flow batteries. The problems with the separators of most all-vanadium flow batteries are: can only meet the requirements of certain aspects of the battery, and cannot obtain a proton conducting membrane with excellent comprehensive properties, such as: the balance between vanadium rejection and conductivity properties. And introducing metal salts with obvious catalytic functions on the positive and negative electrode reactions into two sides of the diaphragm by adopting a step-by-step tape casting method, endowing the diaphragm with a catalytic function, and preparing the composite membrane with the catalytic function. The composite diaphragm prepared by the invention has good vanadium resistance, mechanical property and good performance of a single VRB battery, and can be applied to the field of all-vanadium redox flow batteries.
Description
Technical Field
The invention relates to the field of ion exchange membranes for all-vanadium redox flow batteries (VRB), in particular to a preparation method of a composite membrane with catalytic functions on positive and negative electrodes for all-vanadium redox flow batteries.
Background
The development of new energy sources such as wind energy, solar energy and the like is an important way for solving the shortage of energy resources, and represents the future development direction of energy sources. However, due to time and region dependence, off-grid wind energy and solar energy power generation must use an energy storage system, otherwise, the off-grid wind energy and solar energy power generation cannot be utilized in all weather; and the direct grid connection also needs to adopt an energy storage system to carry out peak load regulation and frequency modulation on the power grid, otherwise, the direct grid connection brings great impact on the power and the frequency of the power grid. Therefore, efficient, large-scale energy storage technology becomes the key core for its development and application.
The vanadium cell (vanadium redox flow battery/Vanadiumredox flow battery) is based on VO2+/VO2 +And V2+/V3+The flow energy storage battery technology of the electric pair is characterized in that energy is stored in electrolyte. Compared with the traditional storage battery, the vanadium battery can be charged and discharged rapidly with large current, has low self-discharge rate, realizes large-capacity storage of energy, is an ideal energy storage form meeting the large-scale energy storage requirements of smart power grids and wind energy and solar power generation, and provides conditions for developing the energy storage technology of the vanadium battery due to the rich vanadium resource advantages in China.
The diaphragm (proton exchange membrane) is one of the key materials and important components of the vanadium battery, is a channel for electrolyte ion transmission, and plays a role in separating the positive electrode and the negative electrode and preventing the short circuit of the battery. Thus, the separator determines to a large extent the coulombic efficiency, the energy efficiency and the cycle life of the vanadium battery. A good proton exchange membrane should have good chemical stability, electrochemical oxidation resistance, low vanadium ion permeability, and low cost. Researchers have conducted extensive research work on VRB membranes, with many beneficial results. However, there are some problems. Can only meet the requirements of certain aspects of the battery, and is difficult to obtain the proton conduction membrane with excellent comprehensive performance. Therefore, how to prepare the high-performance vanadium battery diaphragm material becomes one of the key bottlenecks which restrict the engineering and technical development of the vanadium battery.
Disclosure of Invention
The invention aims to provide a preparation method of a composite membrane with catalytic functions on positive and negative electrodes for an all-vanadium redox flow battery. The composite membrane has good electrical conductivity and ion selective permeability, improves the strength of the membrane, and is suitable for all-vanadium redox flow batteries (VRB).
The technical scheme of the invention is as follows:
a preparation method of a composite membrane with catalytic functions on a positive electrode and a negative electrode for an all-vanadium redox flow battery comprises the following steps and process conditions:
(1) respectively dissolving metal salts with catalytic functions on a positive electrode and a negative electrode in respective solvents, stirring and dissolving to prepare 1-10% by mass of metal salt solution;
(2) dissolving perfluorinated sulfonic acid resin in a high-boiling-point organic solvent, heating and dissolving in a reaction kettle to prepare a perfluorinated sulfonic acid resin solution with the mass percent of 3-25%, wherein the heating and dissolving temperature is 170-260 ℃;
(3) carrying out ultrasonic treatment on the perfluorinated sulfonic acid resin solution obtained in the step (2) to remove bubbles and impurities;
(4) casting the perfluorinated sulfonic acid resin solution obtained in the step (3) on a glass plate by adopting a solution casting method, and volatilizing the solvent into a film at different temperatures of 60-140 ℃ and different time of 0.5-3 h; when the solvent is not completely dried, casting the metal salt solution of the positive electrode in the step (1) onto the membrane for continuous drying;
(5) and (3) inversely placing the membrane prepared in the step (4) on a glass plate, and casting the metal salt solution of the negative electrode in the step (1) onto the membrane for continuous drying for later use.
The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery comprises the step of preparing a high-boiling-point organic solvent from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dichloromethane.
The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery is characterized in that the metal salt is bismuth nitrate, bismuth chloride or tungsten phosphate.
The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery comprises the step (1) of using N, N-dimethylformamide, N-dimethylacetamide, sulfuric acid or acetone as a solvent.
In the preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery, in the step (2), the preferable mass fraction of the perfluorinated sulfonic acid resin solution is 5-15%.
The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery comprises the step (3) of carrying out ultrasonic treatment on a perfluorinated sulfonic acid resin solution for 0.5-4 hours.
The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery comprises the step (4) or the step (5), wherein the membrane preparation drying temperature is 80-140 ℃, and the membrane preparation drying time is 1-4 hours.
The invention has the following advantages and beneficial effects:
1. at present, the most of all-vanadium flow battery separators have the following problems: can only meet the requirements of certain aspects of the battery, and cannot obtain a proton conducting membrane with excellent comprehensive properties, such as: the balance between vanadium rejection and conductivity properties. And introducing metal salts with obvious catalytic functions on the positive and negative electrode reactions into two sides of the diaphragm by adopting a step-by-step tape casting method, endowing the diaphragm with a catalytic function, and preparing the composite membrane with the catalytic function. The composite diaphragm prepared by the invention has good vanadium resistance, mechanical property and good performance of a single VRB battery.
2. The invention scientifically and reasonably designs and combines the diaphragm and the electrode catalyst to construct the composite membrane with catalytic activity, effectively exerts the electrode catalytic function of the catalyst, forms a high-efficiency and stable electrode catalytic reaction interface in the charging and discharging processes of the battery, is beneficial to scientific, safe and effective use of the catalyst, has good ion selective permeability and long-acting positive and negative catalytic activity, and has very important significance for improving the performance of the vanadium battery and reducing the cost of an energy storage system.
Drawings
FIG. 1 shows scanning electron microscopy of composite films (a, surface morphology, b, cross-sectional morphology).
Fig. 2 is a test curve of vanadium ion penetration of Nafion212 and composite membrane.
3(a) -3 (b) are Nafion212, composite film vanadium single cell energy efficiency curve and charge-discharge curve; wherein, fig. 3(a) is an energy efficiency curve; FIG. 3(b) shows a charge/discharge curve.
Detailed Description
The technical means of the present invention will be described in more detail below with reference to examples and drawings.
Example 1
In this embodiment, the specific steps are as follows:
1. dissolving 0.2g of bismuth nitrate in 10mL of N, N-Dimethylformamide (DMF), stirring and dissolving for a negative electrode side catalytic functional layer; 0.15g of tungsten phosphate was dissolved in 10mL of N, N-Dimethylformamide (DMF), and the solution was stirred and dissolved for the positive electrode-side catalytic functional layer.
2. Dissolving 4g of perfluorosulfonic acid resin in N, N-Dimethylformamide (DMF), heating and dissolving in a high-pressure reaction kettle to prepare a perfluorosulfonic acid resin solution with the mass percent of 6%, wherein the heating and dissolving temperature condition is 220 ℃.
3. And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 1h to remove bubbles and impurities.
4. And (3) casting 50mL of the perfluorinated sulfonic acid resin solution obtained in the step (3) on a glass plate by adopting a solution casting method, drying at the temperature of 120 ℃ for 2h to volatilize into a membrane, wherein the thickness of the perfluorinated sulfonic acid resin membrane is 45 mu m, and casting the metal salt solution of the positive electrode obtained in the step (1) on the membrane for continuous drying.
5. And (3) inversely placing the film prepared in the step (4) on a glass plate, and casting the metal salt solution of the negative electrode in the step (1) on the film to be continuously dried for later use.
In this example, the thickness of the obtained composite film was 60 μm, and the contact between the respective interfaces in the composite film was good, and no segmentation occurred.
The relevant performance data for this example is as follows:
as shown in fig. 1, it can be seen from the SEM photograph of the composite membrane that the catalyst is uniformly distributed on the surface and inside of the membrane by the morphological analysis. As shown in FIG. 2, the concentration of VO is 1.5mol/L by using Nafion212 and composite membrane as ion exchange membrane2+Comparison of medium permeability, it can be seen that VO2+The concentration of the ion exchange membrane passing through the ion exchange membrane is increased continuously along with the time, but the permeability of the composite membrane is lower than that of a Nafion212 membrane. In addition, as shown in fig. 3(a) for the VRB single cell test, the energy efficiency of the obtained composite membrane is significantly higher than that of the Nafion212 membrane, and as can be seen from fig. 3(b), under the same current density, the discharge voltage of the VRB single cell using the composite membrane as the ion exchange membrane is higher than that of the Nafion212 membrane, and the charge voltage is lower. Therefore, the catalytic function composite membrane can obviously improve the performance of the battery.
Example 2
The difference from the embodiment 1 is that:
1. dissolving 0.4g of bismuth nitrate in 10mL of N, N-Dimethylformamide (DMF), stirring and dissolving for a negative electrode side catalytic functional layer; 0.3g of tungsten phosphate was dissolved in 10mL of N, N-Dimethylformamide (DMF), and the solution was stirred and dissolved for the positive electrode-side catalytic functional layer.
2. The rest of the procedure was the same as in example 1.
In this example, the thickness of the obtained composite film was 70 μm, and the contact of each interface in the composite film was good, but the uniformity and flatness of the film surface were not good.
Example 3
The difference from the embodiment 1 is that:
1. dissolving 0.1g of bismuth nitrate in 10mL of N, N-Dimethylformamide (DMF), stirring and dissolving for a negative electrode side catalytic functional layer; 0.75g of tungsten phosphate was dissolved in 10mL of N, N-Dimethylformamide (DMF), and the solution was stirred and dissolved for the positive electrode-side catalytic functional layer.
2. The rest of the procedure was the same as in example 1.
In this example, the thickness of the obtained composite film was 55 μm, and the contact between the respective interfaces in the composite film was good, and there was no segmentation phenomenon.
The relevant performance data for this example is as follows:
the coulomb efficiency and energy efficiency of the composite membrane in the all vanadium redox flow battery measured at room temperature are lower than about 2% of the data in the example 1 in the charge-discharge test. The analysis reason is that the catalytic layer is thin and plays a weak catalytic effect.
The experimental results show that: the invention adopts a step-by-step tape casting method to introduce metal salts with obvious catalytic function to the positive and negative electrode reactions into the two sides of the diaphragm to prepare the composite membrane with the catalytic function. The conductivity of the composite diaphragm prepared by the invention meets the use requirement of the vanadium battery, has the advantages of good vanadium resistance, conductivity, good battery performance and the like, and can be widely applied to the field of all-vanadium redox flow batteries.
Claims (6)
1. A preparation method of a composite membrane with catalytic functions for a positive electrode and a negative electrode of an all-vanadium redox flow battery is characterized by comprising the following steps and process conditions:
(1) respectively dissolving metal salts with catalytic functions on a positive electrode and a negative electrode in respective solvents, stirring and dissolving to prepare 1-10% by mass of metal salt solution;
(2) dissolving perfluorinated sulfonic acid resin in a high-boiling-point organic solvent, heating and dissolving in a reaction kettle to prepare a perfluorinated sulfonic acid resin solution with the mass percent of 3-25%, wherein the heating and dissolving temperature is 170-260 ℃;
wherein the high boiling point organic solvent is dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dichloromethane;
(3) carrying out ultrasonic treatment on the perfluorinated sulfonic acid resin solution obtained in the step (2) to remove bubbles and impurities;
(4) casting the perfluorinated sulfonic acid resin solution obtained in the step (3) on a glass plate by adopting a solution casting method, and volatilizing the solvent into a film at different temperatures of 60-140 ℃ and different time of 0.5-3 h; when the solvent is not completely dried, casting the metal salt solution of the positive electrode in the step (1) onto the membrane for continuous drying;
(5) and (3) inversely placing the membrane prepared in the step (4) on a glass plate, and casting the metal salt solution of the negative electrode in the step (1) onto the membrane for continuous drying for later use.
2. The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery according to claim 1, wherein the metal salt is bismuth nitrate, bismuth chloride or tungsten phosphate.
3. The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery according to claim 1, wherein the solvent in the step (1) is N, N-dimethylformamide, N-dimethylacetamide, sulfuric acid or acetone.
4. The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery according to claim 1, wherein in the step (2), the mass fraction of the perfluorinated sulfonic acid resin solution is 5-15%.
5. The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery according to claim 1, wherein in the step (3), the ultrasonic time of the perfluorinated sulfonic acid resin solution is 0.5-4 hours.
6. The preparation method of the composite membrane with the catalytic function for the positive electrode and the negative electrode of the all-vanadium redox flow battery according to claim 1, wherein in the step (4) or the step (5), the membrane preparation and drying temperature is 80-140 ℃ and the time is 1-4 h.
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