CN116706177B - Proton exchange membrane, preparation method thereof and vanadium redox flow battery - Google Patents
Proton exchange membrane, preparation method thereof and vanadium redox flow battery Download PDFInfo
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- CN116706177B CN116706177B CN202310995609.6A CN202310995609A CN116706177B CN 116706177 B CN116706177 B CN 116706177B CN 202310995609 A CN202310995609 A CN 202310995609A CN 116706177 B CN116706177 B CN 116706177B
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- 239000012528 membrane Substances 0.000 title claims abstract description 119
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001690 polydopamine Polymers 0.000 claims abstract description 20
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 56
- 239000012498 ultrapure water Substances 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 42
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 20
- 229960003638 dopamine Drugs 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 14
- 239000004693 Polybenzimidazole Substances 0.000 claims description 13
- 229920002480 polybenzimidazole Polymers 0.000 claims description 13
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 100
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 229920000557 Nafion® Polymers 0.000 description 14
- 229910001456 vanadium ion Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 210000002469 basement membrane Anatomy 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 230000010220 ion permeability Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a proton exchange membrane, a preparation method thereof and a vanadium redox flow battery, belongs to the technical field of new energy, and overcomes the defect that the proton exchange membrane in the prior art is difficult to have high conductivity, good stability and high selectivity. The proton exchange membrane comprises a base membrane and a polydopamine layer coated on the surface of the base membrane; the aperture of a proton transmission channel of the proton exchange membrane is 0.15-0.33 nm, and the free volume fraction is 3.55% -4.30%. The proton exchange membrane has high conductivity, good stability and high selectivity.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a proton exchange membrane, a preparation method thereof and a vanadium redox flow battery.
Background
At present, new energy sources such as solar energy and wind energy, and green novel renewable energy sources are greatly developed worldwide. However, due to the limitation of time, region and other conditions, the generated electric energy is unstable, the continuity is poor and unpredictable, so that the energy storage technology attracts more researchers to find a solution. The matched high-efficiency energy storage system can play a role in regulating peak of a power grid between power generation and power supply, reduce the influence of natural conditions on use, ensure the continuity and stability of new energy power generation and power supply, improve the power generation efficiency and the flexibility of power consumption, and further improve the utilization efficiency of electric energy.
The flow battery is the most ideal energy storage equipment with renewable energy sources, and has the advantages of free site selection, controllable capacity, deep discharge, low self discharge, high efficiency, good safety and the like. One of the large energy storage devices that has been attracting attention and has great promise in recent years is Vanadium Redox Flow Batteries (VRFB). Typically a flow battery system comprises two reservoirs for storing soluble electroactive electrolytes, two electrodes, a membrane and a flow circulation system. The separator is one of the key components of VRFB, which not only affects the cycle performance of the battery, but also plays a decisive role in the economic viability of the overall. The ideal diaphragm has the characteristics of high conductivity, good stability and high selectivity, the current widely applied perfluorosulfonic acid proton exchange membrane Nafon has poor barrier property to vanadium ions, is easy to be corroded by high-acidity and high-corrosivity anode and cathode vanadium solutions, has poor stability, and other proton exchange membranes, such as sulfonated polyether ether ketone, polybenzimidazole, polyimide and the like, have lower conductivity and poor stability compared with Nafion with a fluorocarbon main chain, and become research hot spots.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the proton exchange membrane in the prior art is difficult to have high conductivity, good stability and high selectivity, so as to provide a proton exchange membrane, a preparation method thereof and a vanadium redox flow battery.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the invention provides a proton exchange membrane, which comprises a base membrane and a polydopamine layer coated on the surface of the base membrane;
the aperture of a proton transmission channel of the proton exchange membrane is 0.15-0.33 nm, and the free volume fraction is 3.55% -4.30%.
Further, the thickness of the polydopamine layer is 40-75 nm.
Further, the base film is a perfluorinated sulfonic acid polymer, sulfonated polyether ether ketone or polybenzimidazole.
In a second aspect, the invention provides a preparation method of a proton exchange membrane, wherein a base membrane is soaked in a dopamine alkaline aqueous solution to prepare the proton exchange membrane.
Further, the preparation of the alkaline aqueous solution of dopamine comprises the following steps: dissolving dopamine hydrochloride in tris (hydroxymethyl) aminomethane hydrochloride aqueous solution, and regulating the pH to 7.5-9.5.
Further, in the alkaline aqueous solution of dopamine, the concentration of dopamine hydrochloride is 1g L -1 ~5g L -1 。
Further, the time for soaking the basement membrane in the alkaline aqueous solution of dopamine is 1-8 hours.
Further, tris (hydroxymethyl) aminomethane hydrochloride aqueous solutionThe concentration of tris (hydroxymethyl) aminomethane hydrochloride was 2g L -1 ~ 5g L -1 。
Further, the base film is a perfluorinated sulfonic acid polymer, and is pretreated before being soaked in a dopamine alkaline aqueous solution;
the pretreatment comprises the following steps in sequence:
A. boiling the base film in ultrapure water for 1-2 hours, and cleaning; the base film can absorb water fully and remove dust, greasy dirt, etc.
B. Boiling the base film in hydrogen peroxide solution for 1-2 h, and cleaning; and removing hetero atoms in the base film and oxides on the surface. Preferably, the concentration of the hydrogen peroxide solution is 1-10wt%.
C. Boiling the base film in ultrapure water for 1-2 hours, and cleaning; residual hydrogen peroxide is washed off.
D. Boiling the base film in an acid solution for 1-2 h, and cleaning; the sulfonate groups in the base film are activated. Preferably, the acidic solution is a sulfuric acid solution or a hydrochloric acid solution; the concentration of the acidic solution is 0.5-2 mol/L.
E. Boiling the base film in ultrapure water for 1-2 hours, and cleaning; the remaining acidic solution is washed off.
F. Soaking the base film in sodium chloride aqueous solution for 24-48 h, and replacing hydrogen ions in the base film to prevent the pH of the alkaline solution from being influenced. Preferably, the concentration of the sodium chloride aqueous solution is 0.05-5 mol/L.
Further, the basement membrane is sulfonated polyether ether ketone or polybenzimidazole, and the basement membrane is pretreated before being soaked in alkaline aqueous solution of dopamine;
the pretreatment comprises the following steps in sequence:
(1) Soaking the base film in an acidic solution for 24-48 hours, and cleaning; preferably, the acidic solution is a sulfuric acid solution or a hydrochloric acid solution; the concentration of the acid solution is 0.5-2 mol/L;
(2) Soaking the base film in ultrapure water for 24-48 hours, and cleaning;
(3) And soaking the base film in a sodium chloride aqueous solution for 24-48 h, wherein the concentration of the sodium chloride aqueous solution is preferably 0.05-5 mol/L.
Further, after the basal membrane is soaked in the alkaline aqueous solution of dopamine, the basal membrane is soaked in the acidic solution for 24-48 hours, and then the basal membrane is cleaned. Preferably, the acidic solution is a sulfuric acid solution or a hydrochloric acid solution; the concentration of the acidic solution is 0.5-2 mol/L.
In a third aspect, the invention provides a vanadium redox flow battery comprising the proton exchange membrane or the proton exchange membrane prepared according to the preparation method.
The technical scheme of the invention has the following advantages:
1. the proton exchange membrane provided by the invention comprises a base membrane and a polydopamine layer coated on the surface of the base membrane; the aperture of a proton transmission channel of the proton exchange membrane is 0.15-0.33 nm, and the free volume fraction is 3.55% -4.3%.
In the solution, protons generally exist in the form of hydrated protons, the polydopamine layer is firmly combined on the surface of the base film through the action of hydrogen bonds, and the existence of groups such as phenolic hydroxyl groups, amino groups, imino groups and the like can be combined with water molecules, so that the proton conductivity of the proton exchange film is improved, and the proton conductivity is improved; in addition, the aperture of the proton transmission channel of the proton exchange membrane is reduced due to the existence of the polydopamine layer, which is favorable for inhibiting vanadium ion crossing in the vanadium redox flow battery, thereby improving the selectivity of the proton exchange membrane.
The network structure of the polydopamine layer can inhibit the swelling of the proton exchange membrane, so that the size and the free volume fraction of a proton transmission channel are reduced, the proton exchange membrane is used as a barrier layer to prevent vanadium ions from crossing, the polydopamine layer protects the proton exchange membrane from being corroded by high-concentration and high-oxidation vanadium electrolyte, and the stability of the battery is improved.
2. The thickness of the polydopamine layer of the proton exchange membrane provided by the invention is 40-75 nm. The thickness of the invention can avoid that vanadium ions permeate more due to the too low thickness and the transmission aperture is completely blocked due to the too high thickness, thereby affecting the conductivity of the proton exchange membrane.
3. According to the preparation method of the proton exchange membrane, the base membrane is soaked in the alkaline aqueous solution of dopamine, and the proton exchange membrane is prepared.
Dopamine can readily self-polymerize and oxidize in alkaline solution in the presence of oxygen, forming a thin adherent Polydopamine (PDA) layer on the surface of various inorganic and organic solid materials, such as metals, and self-polymerizing spontaneously to form a uniform and controllable polydopamine layer.
4. The invention provides a preparation method of a proton exchange membrane, wherein the base membrane is a perfluorinated sulfonic acid polymer, and the base membrane is pretreated before being soaked in a dopamine alkaline aqueous solution, and the preparation method sequentially comprises the following steps: A. boiling the base film in ultrapure water for 1-2 hours, and cleaning; B. boiling the base film in hydrogen peroxide solution for 1-2 h, and cleaning; C. boiling the base film in ultrapure water for 1-2 hours, and cleaning; D. boiling the base film in an acid solution for 1-2 h, and cleaning; E. boiling the base film in ultrapure water for 1-2 hours, and cleaning; F. and soaking the base film in a sodium chloride aqueous solution for 24-48 hours.
The pretreatment can wash away the pollutants on the surface of the base film, solvent residues in the film forming process and the like, so that the conductivity and the ion barrier property of the base film are improved. The preparation of the polydopamine layer is carried out under alkaline conditions, hydrogen ions in the base membrane react with hydroxyl ions in the solution to change the pH value of the solution, and the pH value of the solution cannot reach the optimal pH required by the reaction, so that the base membrane is soaked in sodium chloride aqueous solution, and protons in the proton exchange membrane are replaced by ion replacement.
5. According to the preparation method of the proton exchange membrane, after the base membrane is soaked in the alkaline aqueous solution of dopamine, the base membrane is soaked in the acidic solution for 24-48 hours, and then the base membrane is cleaned.
After the polymerization coating of the polydopamine layer is completed, the polydopamine layer is soaked in an acid solution for ion replacement, so that the proton conductivity of the proton exchange membrane is ensured.
The invention provides a self-polymerization reaction modified basal membrane of dopamine, so that the performance of a proton exchange membrane, particularly the vanadium resistance, is improved, on one hand, protons pass through, and on the other hand, vanadium ions are blocked, and the method has a very wide application prospect. The poly-dopamine coating is carried out in water, so that the method is environment-friendly and has simple steps.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of cycle performance;
fig. 2 is self-discharge data at 50% state of charge (SOC) of vanadium redox flow batteries employing proton exchange membranes prepared in example 1 and comparative example 1, respectively.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The Nafion membranes in the examples and comparative examples were Nafion212, sulfonated Polyetheretherketone (SPEEK), polybenzimidazole (PBI), sodium chloride (analytically pure) from fochen chemistry, naOH (analytically pure) from fochen chemistry, tris-HCl buffer (99%) from Alfa Aesar, and dopamine hydrochloride (98%) from Innochem, available from Dupont.
Example 1
The embodiment provides a preparation method of a proton exchange membrane, which comprises the following steps:
1. a piece of 5cm x 5cm Nafion film was boiled in ultrapure water for 1 hour and rinsed 3 times with ultrapure water.
2. Then Nafion film is added with 3wt% of H 2 O 2 Boiling in solution for 1h, and flushing with ultrapure water for 3 times.
3. The Nafion film was boiled in ultrapure water for 1 hour and rinsed 3 times with ultrapure water.
4. The Nafion film was boiled in 1M dilute sulfuric acid for 1h and rinsed 3 times with ultrapure water.
5. The Nafion film was boiled in ultrapure water for 1 hour and rinsed 3 times with ultrapure water.
6. The Nafion membrane was placed in 100ml of ultrapure water, and 0.585g (0.01 mol) of sodium chloride solid was added, and after dissolution of sodium chloride, it was shaken on a shaker for 24 hours.
7. 100ml of ultrapure water was taken in a beaker, 0.3152g (0.002 mol) tris-HCl and 0.3792g (0.002 mol) dopamine hydrochloride were added, naOH was added to adjust the pH to 8.5, nafion membrane was put in the prepared solution, and after 2 hours of reaction, the solution was taken out and washed with ultrapure water several times to prepare a proton exchange membrane.
8. The proton exchange membrane was immersed in 1M dilute sulfuric acid for 24h, and the solution was changed 2 times in the middle.
9. And then the proton exchange membrane is washed 3 times by ultrapure water, soaked in the ultrapure water for 24 hours, and the ultrapure water is replaced for 2 times in the middle.
Example 2
The embodiment provides a preparation method of a proton exchange membrane, which comprises the following steps:
1. a piece of 5cm SPEEK film was immersed in 1M dilute sulfuric acid for 24h, the solution was changed 2 times in the middle, and the SPEEK film was rinsed 3 times with ultra pure water.
2. The SPEEK film was then immersed in ultrapure water for 24 hours, and the ultrapure water was replaced 2 times in the middle.
3. The SPEEK film was then placed in 100ml of ultra pure water and 0.585g of sodium chloride solid was added and, after dissolution of the sodium chloride, shaken on a shaker for 24h.
4. Taking 100ml of ultrapure water in a beaker, adding 0.3152g of tris-HCl and 0.3792g of dopamine hydrochloride, adding NaOH to adjust the pH to 8.5, putting the SPEEK membrane into the prepared solution, taking out the membrane after 2h of reaction, and flushing the membrane with ultrapure water for a plurality of times to prepare the proton exchange membrane.
5. The proton exchange membrane was immersed in 1M dilute sulfuric acid for 24h, and the solution was changed 2 times in the middle.
6. The SPEEK film was rinsed 3 times with ultrapure water, immersed in ultrapure water for 24 hours, and replaced 2 times in the middle.
Example 3
The embodiment provides a preparation method of a proton exchange membrane, which comprises the following steps:
1. a piece of 5cm x 5cm PBI film was taken, immersed in 1M dilute sulfuric acid for 24 hours, the solution was changed 2 times in the middle, and the PBI film was rinsed 3 times with ultrapure water.
2. The PBI membrane was immersed in ultrapure water for 24 hours, and the ultrapure water was replaced 2 times during the process.
3. The PBI membrane was then placed in 100ml of ultrapure water, and 0.585g of sodium chloride solid was added thereto, and after dissolution of sodium chloride, the membrane was shaken on a shaker for 24 hours.
4. Taking 100ml of ultrapure water in a beaker, adding 0.3152g of tri-HCl and 0.3792g of dopamine hydrochloride, adding NaOH to adjust the pH to 8.5, putting the PBI membrane into the prepared solution, taking out the membrane after 2h of reaction, and flushing the membrane with ultrapure water for a plurality of times to obtain the proton exchange membrane.
5. Before the test, the proton exchange membrane is soaked in 1M dilute sulfuric acid for 24 hours, and the solution is replaced for 2 times in the middle.
6. The PBI membrane was rinsed 3 times with ultrapure water, immersed in ultrapure water for 24 hours, and replaced 2 times in the middle.
Example 4
The present embodiment is basically the same as embodiment 2, except that step 4 is: taking 100ml of ultrapure water in a beaker, adding 0.2g of tris-HCl and 0.1g of dopamine hydrochloride, adding NaOH to adjust the pH to 7.5, putting the SPEEK membrane into the prepared solution, taking out the membrane after reacting for 1h, and flushing the membrane with ultrapure water for a plurality of times to prepare the proton exchange membrane.
Example 5
The present embodiment is basically the same as embodiment 2, except that step 4 is: taking 100ml of ultrapure water in a beaker, adding 0.5g of tris-HCl and 0.5g of dopamine hydrochloride, adding NaOH to adjust the pH to 9.5, putting the SPEEK membrane into the prepared solution, taking out the membrane after reaction for 8 hours, and flushing the membrane with ultrapure water for a plurality of times to prepare the proton exchange membrane.
Comparative example 1
The embodiment provides a preparation method of a proton exchange membrane, which comprises the following steps:
1. a piece of 5cm x 5cm Nafion film was taken, boiled with ultrapure water for 1h, and rinsed 3 times with ultrapure water.
2 Nafion film was then dried at 3wt% H 2 O 2 Boiling in solution for 1h, and flushing with ultrapure water for 3 times.
3. The Nafion film was boiled in ultrapure water for 1 hour and rinsed 3 times with ultrapure water.
4. The Nafion film was boiled in 1M dilute sulfuric acid for 1h and rinsed 3 times with ultrapure water.
5. The Nafion film was boiled in ultrapure water for 1 hour and rinsed 3 times with ultrapure water.
Comparative example 2
This comparative example is substantially the same as example 2, except that step 4 is: taking 100ml of ultrapure water in a beaker, adding 0.5g of tris-HCl and 1g of dopamine hydrochloride, adding NaOH to adjust the pH to 8.5, putting the SPEEK membrane into the prepared solution, taking out the membrane after reacting for 8 hours, and flushing the membrane with ultrapure water for a plurality of times to obtain the proton exchange membrane.
Test example 1
(1) The proton conductivity test method of the proton exchange membrane comprises the following steps:
cutting proton exchange membrane into strips with width of about 1 cm, and controlling water temperature of water bath kettle to 25 o And C, connecting the proton exchange membrane with a clamp of the four electrodes, soaking in ultrapure water for more than half an hour, and repeatedly measuring the alternating current impedance of the proton exchange membrane when the proton exchange membrane is stable, wherein a proton conductivity calculation formula is shown in a formula 1.
1 (1)
Where L is the width of two electrodes in the four electrode fixture, which is 0.5 cm, and R, d and h represent the alternating current impedance (Ω), film width (cm) and film thickness (mm), respectively.
(2) Vanadium ion permeability test method
In vanadiumIn the infiltration mold, the left side was 1.5M MgSO 4 And 3M H 2 SO 4 Mixed solution 50 mL; right side is 1.5M VOSO 4 And 3M H 2 SO 4 Mixed solution 50 mL; the two solutions were magnetically stirred continuously to avoid concentration polarization. And taking out the solution from the left solution at regular intervals, putting the solution into a cuvette, and putting the cuvette into an ultraviolet spectrophotometer to measure the concentration of vanadium ions. The vanadium ion permeability calculation method is shown in the formula 2.
2, 2
Wherein C is 1 (t) is the concentration of vanadium ions to be detected on the right side at the permeation time t, and the unit is mmolL -1 ；C 2 (t) is the concentration of vanadium ions to be detected on the left side, and the unit is mmolL -1 ；V 2 Is the left volume in cm 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the effective area of the film to be measured, and the unit is cm 2 The method comprises the steps of carrying out a first treatment on the surface of the L is the thickness of the proton exchange membrane to be measured, and the unit is cm; p is the permeability of vanadium ions in cm 2 min -1 。
The test results are shown in Table 1.
TABLE 1 proton exchange Membrane parameters
According to the invention, as shown in the embodiment 1 and the comparative example 1, the polydopamine layer is coated on the surface of the base membrane, so that the conduction of protons on the membrane surface is promoted, and the conductivity of the proton exchange membrane can be well improved by more than 15%; meanwhile, the polydopamine layer attached to the surface of the base film reduces the proton transmission channel of the proton exchange film, reduces the free volume fraction, improves the vanadium resistance of the proton exchange film, and reduces the vanadium ion permeability by more than 80%.
By combining the analysis of the results, the polymerized dopamine on the surface of the proton exchange membrane can effectively improve the performance of the proton exchange membrane, especially the relative selectivity of the proton exchange membrane, so that the energy efficiency of the flow battery is improved.
(3) Method for testing cycle performance
The proton exchange membrane was sandwiched between two graphite felt electrodes (activated overnight at 475 ℃ C.) and had an effective area of 4cm -2 And then placed between two graphite plates engraved with serpentine flow fields. The electrolytes used for the negative electrode and the positive electrode were 15 mL of 1.5M V 3+ (3 M H 2 SO 4 ) And 1.5M VO 2+ (3 M H 2 SO 4 ) By N 2 Purging at 40 mL min -1 Is provided. Battery performance was monitored by the LAND battery test system (CT 2001B). The cut-off voltage was controlled at 1.6V and 0.8V to avoid side reactions.
The process for testing the cycle performance comprises the following steps: at 80mA cm -2 And (5) performing charge and discharge circulation at 0.8-1.6V. The test results are shown in FIG. 1.
Fig. 2 is self-discharge data at 50% state of charge (SOC) of vanadium redox flow batteries employing proton exchange membranes prepared in example 1 and comparative example 1, respectively.
As can be seen from fig. 1 and 2, the cycle performance of the vanadium redox flow battery can be greatly improved by adopting the proton exchange membrane of the invention. Obviously, the existence of the polydopamine layer protects the proton exchange membrane from being corroded by the high-concentration and high-oxidation vanadium electrolyte, so that the cycle times and the service time of the battery are effectively improved, and the stability of the battery is improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (8)
1. The vanadium redox flow battery is characterized by comprising a proton exchange membrane;
the proton exchange membrane consists of a base membrane and a polydopamine layer coated on the surface of the base membrane;
the aperture of a proton transmission channel of the proton exchange membrane is 0.15-0.33 nm, and the free volume fraction is 3.55-4.30%;
the base film is a perfluorinated sulfonic acid polymer, sulfonated polyether ether ketone or polybenzimidazole;
the thickness of the polydopamine layer is 40-75 nm;
the preparation method of the proton exchange membrane comprises the following steps: soaking the base membrane in a dopamine alkaline aqueous solution to prepare the proton exchange membrane;
when the base film is a perfluorinated sulfonic acid polymer, the base film is pretreated before being soaked in a dopamine alkaline aqueous solution;
the pretreatment comprises the following steps in sequence:
A. boiling the base film in ultrapure water for 1-2 h, and cleaning;
B. boiling the base film in hydrogen peroxide solution for 1-2 h, and cleaning;
C. boiling the base film in ultrapure water for 1-2 h, and cleaning;
D. boiling the base film in an acid solution for 1-2 h, and cleaning;
E. boiling the base film in ultrapure water for 1-2 h, and cleaning;
F. soaking the base film in sodium chloride water solution for 24-48 h;
when the base film is sulfonated polyether ether ketone or polybenzimidazole, the base film is pretreated before being soaked in alkaline aqueous solution of dopamine; the pretreatment comprises the following steps in sequence:
(1) Soaking the base film in an acidic solution for 24-48 h, and cleaning;
(2) Soaking the base film in ultrapure water for 24-48 hours, and cleaning;
(3) Soaking the base film in sodium chloride water solution for 24-48 h;
the acid solution is sulfuric acid solution or hydrochloric acid solution;
soaking the basal membrane in an alkaline aqueous solution of dopamine, soaking the basal membrane in an acidic solution for 24-48 h, and cleaning.
2. The vanadium redox flow battery of claim 1, wherein said preparation of said aqueous alkaline solution of dopamine comprises: the dopamine hydrochloride is dissolved in tris (hydroxymethyl) aminomethane hydrochloride aqueous solution and the pH is adjusted to 7.5-9.5.
3. The vanadium redox flow battery of claim 2, wherein the concentration of dopamine hydrochloride in said aqueous alkaline solution is 1g L -1 ～5g L -1 。
4. The vanadium redox flow battery of claim 2, wherein the base membrane is immersed in the alkaline aqueous solution of dopamine for a period of time ranging from 1h to 8h.
5. The vanadium flow battery of claim 2, wherein the concentration of tris (hydroxymethyl) aminomethane hydrochloride in the tris (hydroxymethyl) aminomethane hydrochloride aqueous solution is 2g L -1 ～5g L -1 。
6. The vanadium redox flow battery of claim 1, wherein the concentration of the acidic solution is 0.5-2 mol/L.
7. The vanadium redox flow battery of claim 1, wherein the concentration of the hydrogen peroxide solution is 1-10 wt%.
8. The vanadium redox flow battery of claim 1, wherein the concentration of the aqueous sodium chloride solution is 0.05-5 mol/L.
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