CN115763921A - Proton exchange membrane with self-healing capability and preparation method thereof - Google Patents
Proton exchange membrane with self-healing capability and preparation method thereof Download PDFInfo
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- CN115763921A CN115763921A CN202211301529.8A CN202211301529A CN115763921A CN 115763921 A CN115763921 A CN 115763921A CN 202211301529 A CN202211301529 A CN 202211301529A CN 115763921 A CN115763921 A CN 115763921A
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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
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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
Abstract
The invention relates to the technical field of hydrogen fuel cells, and discloses a proton exchange membrane with self-healing capability and a preparation method thereof, wherein the exchange membrane is prepared from the following components: the alcohol polymer comprises alcohol polymer solids, deionized water, a Nafion solution and 5% dilute sulfuric acid, wherein the alcohol polymer solids comprise the following components in parts by mass: 20-50 parts of alcohol polymer solid, 40-60 parts of deionized water, 10-20 parts of Nafion solution and 10-20 parts of 5% dilute sulfuric acid. According to the proton exchange membrane provided by the invention, when the proton membrane is damaged when the junction of the proton membrane and the frame is stimulated by different stresses, a large amount of hydrogen bonds are formed between the alcohol polymer and between the alcohol polymer and Nafion under the environment of the membrane electrode by giving set pressure and humidity to the proton membrane at the junction, and under the set pressure, good proton membrane self-repairing is realized, so that the repair of the damaged position of the proton membrane is completed.
Description
Technical Field
The invention relates to the technical field of hydrogen fuel cells, in particular to a proton exchange membrane with self-healing capability and a preparation method thereof.
Background
A hydrogen fuel cell is a power generation device that converts chemical energy into electrical energy, and hydrogen and oxygen are converted into electrical energy by the hydrogen fuel cell device, with the product being water. The hydrogen fuel cell has the advantages of zero pollution, high energy density, quick start and the like, is a green energy technology, can effectively relieve the problems of energy shortage and environmental pollution faced by the world at present, and has wide application prospect under the large background of carbon peak reaching and carbon neutralization.
A membrane electrode assembly (mea) is a key component of a hydrogen fuel cell, and is a place where chemical energy is converted into electrical energy, so that the life thereof is important for the life of the entire hydrogen fuel cell. Typically, the membrane electrode consists of seven parts, a proton exchange membrane (proton exchange membrane) located in the center of the membrane electrode, a cathode and anode catalyst layer (catalyst layer) on both sides of the proton exchange membrane, a frame (frame) on both sides for sealing, and a gas diffusion layer (gas diffusion layer) for gas transmission. Through failure analysis of the membrane electrode, people find that cracks are easy to occur at the contact position of the proton exchange membrane and the frame due to the fact that stress of the proton exchange membrane changes periodically along with working conditions, and finally the proton exchange membrane is perforated and perforated. The proton membrane is perforated and holed, which can cause the cross phenomenon of the reaction gas at the two sides of the cathode and the anode, which not only can lead the performance of the membrane electrode to be reduced, but also has huge potential safety hazard.
The invention patent application No. 201510401489.8 discloses a proton exchange membrane with self-repairing capability and a preparation method thereof. The proton exchange membrane with the self-repairing capability is prepared by compounding self-repairing materials and proton conducting materials through methods such as blending, copolymerization and interpenetrating polymer networks, and then preparing a membrane in a blade coating and pouring membrane forming manner. But the self-repairing capability of the technology is weak, and the repairing area cannot be well repaired.
Application number 201610824068.0 the present invention discloses a polyvinyl alcohol film with self-repairing function by dynamic covalent bond and its preparation method. Carrying out grafting reaction on polyvinyl alcohol and furan derivatives to obtain furan ring graft modified polyvinyl alcohol, then adding a cross-linking agent which can carry out Diels-Alder reaction with furan groups, and carrying out Diels-Alder reaction, thereby obtaining the polyvinyl alcohol film with the self-repairing function. The membrane can be applied to the field of proton exchange membrane fuel cells. The raw materials used in the technology have set toxicity and are not friendly to the environment.
The invention patent with the application number of 201810000754.5 discloses a repairable compound proton exchange membrane and a preparation method thereof. The proton conduction agent and the methanol blocking agent are dissolved in the solvent and are uniformly mixed. Concentrating at 60-100 deg.C, vacuum drying at 50-80 deg.C for 1-5 hr, soaking in stabilizer for 1-20 hr, and drying for 5-8 hr. The repairable composite proton exchange membrane is obtained by controlling the temperature and the steps. However, the technology is applied to the technical field of methanol fuel cells, the process is complex, the time consumption is long, and industrialization is difficult to realize.
The invention patent application No. 2018100222046 discloses an inorganic-organic self-repairing fuel cell proton exchange membrane and a preparation method thereof. The invention selects inorganic self-repairing base and proton conducting material, homogenizes by a rotary homogenizer and a pressure homogenizer, and obtains the proton exchange membrane with self-repairing capability after casting and film forming. The membrane can overcome the swelling of the proton exchange membrane at high temperature, and the service life is prolonged. However, at high temperatures, the main failure mode of proton exchange membranes is due to the decrease in proton transfer efficiency caused by water deficiency, and the swelling phenomenon at high temperatures is not significant.
At present, the self-repairing proton exchange membrane is mostly aimed at the technical field of methanol fuel cells, and the field of hydrogen fuel cells is rarely reported. The disadvantages or self-healing capabilities of such techniques are poor; or not environmentally friendly; or the preparation process is complex and takes long time, which is difficult to realize for industrialization; or not in the field of hydrogen fuel cells. Therefore, the invention provides a proton exchange membrane with self-healing capability and a preparation method thereof.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a proton exchange membrane with self-healing capability and a preparation method thereof, aiming at solving the problem that the junction between the proton membrane and a frame is damaged due to frequent dry-wet working condition conversion in the practical application process of the proton exchange membrane, so that the proton conduction and the mechanical performance are invalid.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a proton exchange membrane with self-healing capability is prepared from the following components: the adhesive comprises alcohol polymer solids, deionized water, a Nafion solution and 5% dilute sulfuric acid, wherein the alcohol polymer solids comprise the following components in parts by mass: 20-50 parts of alcohol polymer solid, 40-60 parts of deionized water, 10-20 parts of Nafion solution and 10-20 parts of 5% dilute sulfuric acid.
Preferably, the solid content of the Nafion solution is 5% to 10%.
A preparation method of a proton exchange membrane with self-healing capability comprises the following steps:
the first step is as follows: dissolving solid alcohol polymer in deionized water, and heating in water bath;
the second step: coating a Nafion solution with solid content of 5-10% on a glass plate by a blade coating or slit coating method, and drying to obtain a Nafion film;
the third step: coating the prepared alcohol polymer solution on a dried Nafion film in a blade coating or slit coating mode, and drying;
the fourth step: coating the Nafion solution with the solid content of 5% on the dried alcohol polymer film in a blade coating or slit coating mode, drying, and preparing the self-healing proton exchange membrane;
the fifth step: and (4) acidizing, standing at room temperature for drying, carrying out a self-repairing experiment on the obtained self-healing proton exchange membrane, and testing the proton conductivity of the self-healing proton exchange membrane.
Preferably, the heating condition of the water bath in the first step is 70-100 ℃ for 1-5h.
Preferably, the drying condition in the second step is drying in an oven at 150 ℃ for 1-5h.
Preferably, the drying condition in the third step is drying in an oven at 70-100 ℃ for 1-5h.
Preferably, the drying condition in the fourth step is drying for 1-5h in an oven at 70-100 ℃.
Preferably, the acidification treatment in the fifth step is to soak the prepared proton exchange membrane in dilute sulfuric acid for 1-2h.
(III) advantageous effects
Compared with the prior art, the proton exchange membrane with self-healing capability and the preparation method thereof provided by the invention have the following beneficial effects:
1. the proton exchange membrane with the self-healing capability and the preparation method thereof have the advantages of strong self-healing capability, environmental friendliness, simple and easy preparation process and can be applied to the technical field of hydrogen fuel cells.
2. The proton exchange membrane with the self-healing capability and the preparation method thereof can be applied to roll-to-roll industrial coating equipment, and meet the requirement of large-scale production.
Drawings
FIG. 1 is a schematic view of a proton exchange membrane of the present invention;
fig. 2 is a comparison graph before and after the self-healing of the proton membrane.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, the embodiments of the proton exchange membrane with self-healing capability and the preparation method thereof provided by the present invention refer to examples 1-3 below.
Example 1
The proton exchange membrane with the self-healing capability provided by the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the proton exchange membrane with the self-healing capability comprises the following specific steps:
step 1: preparing an alcohol polymer solution, dissolving a solid alcohol polymer in deionized water, heating in a water bath at 70-100 ℃ for 1-5h.
Step 2: coating the Nafion solution with 5% solid content on a glass plate by a knife coating or slit coating method, and drying for 1-5h at 150 ℃ in an oven.
And 3, step 3: coating the prepared alcohol polymer solution on a dried Nafion membrane in a blade coating or slit coating mode, and drying for 1-5h at 70-100 ℃ in an oven.
And 4, step 4: coating the solution on the dried alcohol polymer film by blade coating or slit coating of 5% solid content Nafion solution, drying in an oven at 70-100 deg.C for 1-5h, and self-healing to obtain the final product
And 5: soaking the prepared proton exchange membrane in dilute sulfuric acid for 1-2h, carrying out acidification treatment, and then standing at room temperature for drying. And carrying out a self-repairing experiment on the obtained self-healing proton exchange membrane, and testing the proton conductivity of the self-healing proton exchange membrane.
Example 2
The proton exchange membrane with the self-healing capability provided by the embodiment is prepared from the following raw materials in parts by weight:
| alcohol polymerSolid body | 50 parts of a binder; |
| deionized water | 40 parts of a mixture; |
| 5% -10% of Nafion solution | 10 parts of (A); |
| 5% dilute sulfuric acid | 20 parts of (1); |
the preparation method of the proton exchange membrane with the self-healing capability comprises the following specific steps:
step 1: preparing an alcohol polymer solution, dissolving a solid alcohol polymer in deionized water, heating in a water bath at 70-100 ℃ for 1-5h.
Step 2: coating the Nafion solution with 5% solid content on a glass plate by a knife coating or slit coating method, and drying for 1-5h at 150 ℃ in an oven.
And 3, step 3: coating the prepared alcohol polymer solution on a dried Nafion film in a blade coating or slit coating mode, and drying for 1-5h at 70-100 ℃ in an oven.
And 4, step 4: coating the solution on the dried alcohol polymer film by blade coating or slit coating of 5% solid content Nafion solution, drying in an oven at 70-100 deg.C for 1-5h, and self-healing to obtain the final product
And 5: soaking the prepared proton exchange membrane in dilute sulfuric acid for 1-2h, carrying out acidification treatment, and then standing at room temperature for drying. And carrying out a self-repairing experiment on the self-healing proton exchange membrane, and testing the proton conductivity of the self-healing proton exchange membrane.
Example 3
The proton exchange membrane with the self-healing capability provided by the embodiment is prepared from the following raw materials in parts by weight:
| alcohol polymer solid | 15 parts of (1); |
| deionized water | 45 parts of a binder; |
| 5% -10% of Nafion solution | 15 parts of (1); |
| 5% dilute sulfuric acid | 18 parts of a mixture; |
the preparation method of the proton exchange membrane with the self-healing capability comprises the following specific steps:
step 1: preparing an alcohol polymer solution, dissolving a solid alcohol polymer in deionized water, heating in a water bath at 70-100 ℃ for 1-5h.
And 2, step: coating the Nafion solution with 5% solid content on a glass plate by a knife coating or slit coating method, and drying for 1-5h at 150 ℃ in an oven.
And step 3: coating the prepared alcohol polymer solution on a dried Nafion membrane in a blade coating or slit coating mode, and drying for 1-5h at 70-100 ℃ in an oven.
And 4, step 4: coating the solution on the dried alcohol polymer film by blade coating or slit coating of 5% solid content Nafion solution, drying in an oven at 70-100 deg.C for 1-5h, and self-healing to obtain the final product
And 5: soaking the prepared proton exchange membrane in dilute sulfuric acid for 1-2h, carrying out acidification treatment, and then standing at room temperature for drying. And carrying out a self-repairing experiment on the obtained self-healing proton exchange membrane, and testing the proton conductivity of the self-healing proton exchange membrane.
The proton exchange membrane for realizing the self-healing capability by utilizing the hydrogen bonds has the advantages that the self-healing is required to be carried out under proper external stimulation, the environmental humidity and the external pressure are required to be set, the conditions can be met in the actual use process of the membrane electrode, the membrane electrode does not need to be disassembled, and therefore the repairing process is simple and easy to implement.
The self-healing performance is realized by the following processes: according to the proton exchange membrane provided by the invention, when the proton membrane is damaged when the junction of the proton membrane and the frame is stimulated by different stresses, a large amount of hydrogen bonds are formed between the alcohol polymer and between the alcohol polymer and Nafion under the environment of the membrane electrode by giving set pressure and humidity to the proton membrane at the junction, and under the set pressure, good proton membrane self-repairing is realized, so that the repair of the damaged position of the proton membrane is completed.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A proton exchange membrane with self-healing capability is characterized by being prepared from the following components: the alcohol polymer comprises alcohol polymer solids, deionized water, a Nafion solution and 5% dilute sulfuric acid, wherein the alcohol polymer solids comprise the following components in parts by mass: 20-50 parts of alcohol polymer solid, 40-60 parts of deionized water, 10-20 parts of Nafion solution and 10-20 parts of 5% dilute sulfuric acid.
2. A proton exchange membrane with a self-healing capability according to claim 1, wherein: the solid content of the Nafion solution is 5-10%.
3. A method for preparing a proton exchange membrane with self-healing capability according to claim 1 or 2, comprising the following steps:
the first step is as follows: dissolving solid alcohol polymer in deionized water, and heating in water bath;
the second step is that: coating a Nafion solution with solid content of 5-10% on a glass plate by a blade coating or slit coating method, and drying to obtain a Nafion film;
the third step: coating the prepared alcohol polymer solution on a dried Nafion film in a blade coating or slit coating mode, and drying;
the fourth step: coating the Nafion solution with the solid content of 5% on the dried alcohol polymer film in a blade coating or slit coating mode, drying, and preparing the self-healing proton exchange membrane;
the fifth step: and (4) carrying out acidification treatment, then standing at room temperature for drying, carrying out a self-repairing experiment on the obtained self-healing proton exchange membrane, and testing the proton conductivity of the self-healing proton exchange membrane.
4. The production method according to claim 3, characterized in that: the heating condition of the water bath in the first step is heating the mixture in the water bath for 1 to 5 hours at the temperature of between 70 and 100 ℃.
5. The production method according to claim 3, characterized in that: the drying condition in the second step is drying in an oven at 150 ℃ for 1-5h.
6. The production method according to claim 3, characterized in that: the drying condition in the third step is drying in an oven at 70-100 ℃ for 1-5h.
7. The production method according to claim 3, characterized in that: the drying condition in the fourth step is drying for 1-5h in an oven at 70-100 ℃.
8. The production method according to claim 3, characterized in that: and the acidification treatment in the fifth step is to soak the prepared proton exchange membrane in dilute sulfuric acid for 1-2h.
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