CN110504474B - Method for preparing heterogeneous composite proton exchange membrane by regulating and controlling interface microstructure - Google Patents
Method for preparing heterogeneous composite proton exchange membrane by regulating and controlling interface microstructure Download PDFInfo
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- CN110504474B CN110504474B CN201910787420.1A CN201910787420A CN110504474B CN 110504474 B CN110504474 B CN 110504474B CN 201910787420 A CN201910787420 A CN 201910787420A CN 110504474 B CN110504474 B CN 110504474B
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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
- H01M8/10—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
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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
- H01M8/10—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
- H01M8/1076—Micromachining techniques, e.g. masking, etching steps or photolithography
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a method for preparing a heterogeneous composite proton exchange membrane by regulating and controlling an interface microstructure, which comprises the steps of preparing a single-side micropatterned substrate by template transfer; and then, removing the template by using a template remover to obtain the matrix with the adjustable and controllable micro-pattern. And secondly, coating an ionomer with high proton conductivity on the side with the micro-pattern, and drying to obtain the heterogeneous heterostructure composite proton exchange membrane with excellent interface binding force. The proton conductivity of the heterostructure composite PEM prepared by the invention is obviously improved in a full hydration test state, the proton conductivity is improved by nearly 1.1 times compared with that of a pure matrix at the temperature of 80 ℃, and the heterostructure composite PEM is simple in preparation method, wide in application range and beneficial to large-scale commercial production.
Description
Technical Field
The invention belongs to the field of proton exchange membranes, and relates to a method for preparing a heterogeneous composite proton exchange membrane by regulating and controlling an interface microstructure.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are generally composed of bipolar plates, gas diffusion layers, catalyst layers, and a Proton Exchange Membrane (PEM). Among them, the PEM is one of the core components of the PEMFC, and requires high chemical and thermal stability, good mechanical properties, high proton conductivity, low fuel permeability, etc. to meet the application requirements.
The anode of the fuel cell is typically selectively fed with humidified H2As fuel, H obtained by oxidation of lost electrons under the action of catalyst+The electrons transported to the cathode through PEM and oxygen and external circuit generate O2To produce water. It can be seen that the anode of the fuel cell requires water to ensure proton transport in the PEM, while the cathode needs to drain the generated water in time, and therefore the PEM should be designed as a heterostructure membrane with hydrophilic anode side and hydrophobic cathode side; but the PEM currently commercialized is still a homogeneous membrane.
At present, perfluorosulfonic acid PEM represented by Nafion is widely used in PEMFCs, but the perfluorosulfonic acid membrane is expensive and has a high fuel leakage rate. In recent years, in order to solve the above problems, researchers have studied to have a higher glass transition temperature (T)g) And chemically stableHydrocarbon-based polymers such as: polysulfone (PSF), Polybenzimidazole (PBI), Polyimide (PI), or Polyetheretherketone (PEEK), and the like. However, these polymers must be sulfonated or doped with phosphoric acid to be used as PEM, and there is Trade-off effect between the mechanical property and proton conductivity due to the introduction of functional groups. Therefore, to balance the relationship of mechanical properties with proton conductivity, researchers have prepared various hybrid PEMs based on hydrocarbon groups.
The compounding method is a method for preparing the multilayer composite PEM by simply, conveniently and quickly modifying the commercial membrane. The method has the advantages that the asymmetric membrane with the heterogeneous structure can be prepared, and the method has great application prospect in a salt difference battery, a vanadium fluid battery and a proton exchange membrane fuel cell. The recombination of the weak interface interaction force exists, the problems of large interface resistance and easy falling exist, and the output of the PEMFC in high power density and long cycle life are influenced. Based on the above, Hee-Tak Kim et al (adv. Mater.2017,29,1603056) prepare three-dimensional interlocked perfluorosulfonic acid/polysulfone/perfluorosulfonic acid composite PEM by a template removal method, and tests show that the prepared composite membrane has low impedance and good cycling stability. However, how to prepare a heterostructure composite PEM with good interfacial compatibility on a large scale is still a problem to be solved.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing a heterogeneous composite proton exchange membrane by regulating and controlling an interface microstructure, which solves the problems of PEM proton conductivity reduction and swelling rate increase caused by different reaction characteristics of a cathode and an anode of the proton exchange membrane.
Technical scheme
A method for preparing a heterogeneous composite proton exchange membrane by regulating and controlling an interface microstructure is characterized by comprising the following steps:
step 1, preparing a single-layer opal structure photonic crystal: placing a dry microsphere between two pieces of polydimethylsiloxane PDMS to enable the two pieces of polydimethylsiloxane PDMS to generate friction, and under the induction of the action of electrostatic force, self-assembling the microsphere on the polydimethylsiloxane PDMS substrate positioned at the bottom to form a single-layer microsphere array as a micropattern;
step 2, preparing a single-side patterned proton exchange membrane substrate: pouring a solution of a polycarbonyl ionomer on the surface of the micro pattern, placing the solution in a vacuum drying oven, placing the solution for 60 to 12 hours to volatilize a solvent until the solution is dried at the temperature of between 30 and 60 ℃, placing one side of the template embedded with the micro pattern in a template remover to remove the template, and obtaining a substrate with the micro pattern structure being a reflector crystal structure or a bicontinuous microstructure and the micro pattern on one side;
the concentration of the solution of the polycarbonyl ionomer is 0.1-0.5 g/ml;
step 3, preparation of the heterostructure composite proton exchange membrane: coating an ionomer with high proton conductivity on one side with the micro pattern, and drying in a vacuum drying oven to obtain a heterostructure composite PEM with good interface compatibility; the concentration of the ionomer is 0.12-0.3 g/ml.
The microspheres are: polystyrene PS, polymethyl methacrylate PMMA or silicon dioxide SiO2And (3) microspheres.
The particle size of the microsphere is as follows: 500 nm-5 μm.
The polymer hydrocarbon-based ionomer is one or more than two of sulfonated polysulfone or sulfonated polyether ether ketone; the sulfonation degree of the sulfonated polysulfone is 20-50%; the sulfonation degree of the sulfonated polyether-ether-ketone is 10-50%.
The template remover is toluene, tetrahydrofuran or hydrofluoric acid solution.
The scraping ionomer is sulfonated POSS ionomer, sulfonated polyether ether ketone or Nafion solution; the sulfonation degree of the sulfonated polysulfone or the sulfonated polyether ether ketone is more than 60 percent.
Advantageous effects
The invention provides a method for preparing a heterogeneous composite proton exchange membrane by regulating an interface microstructure, which comprises the steps of preparing a single-side micropatterned substrate by template transfer; and then, removing the template by using a template remover to obtain the matrix with the adjustable and controllable micro-pattern. And secondly, coating an ionomer with high proton conductivity on the side with the micro-pattern, and drying to obtain the heterogeneous heterostructure composite proton exchange membrane with excellent interface binding force. The proton conductivity of the heterostructure composite PEM prepared by the invention is obviously improved in a full hydration test state, the proton conductivity is improved by nearly 1.1 times compared with that of a pure matrix at the temperature of 80 ℃, and the heterostructure composite PEM is simple in preparation method, wide in application range and beneficial to large-scale commercial production.
Aiming at different characteristics of the cathode and the anode of the PEMFC, the heterostructure composite PEM is an ionomer with good water absorption close to the anode side, the cathode side adopts a more hydrophobic and more mechanical stable polycarbohydride ionomer with low fuel permeability, and the heterostructure composite PEM has good interface compatibility by designing micro-patterning of an interface.
Compared with the prior materials and technologies, the invention has the following advantages:
1) the heterostructure composite PEM prepared by the preparation method provided by the invention can enhance the adaptability under different reaction conditions of the anode and the cathode;
2) the proton conductivity of the composite PEM prepared by the method is obviously improved in a full hydration test state, and the proton conductivity is improved by about 1.1 times compared with that of a pure sulfonated polysulfone matrix at 80 ℃;
3) the preparation method is simple, can carry out post-treatment modification on the existing commercial membrane, and is beneficial to large-scale commercial production.
Drawings
FIG. 1 is a surface electron micrograph of a substrate of one-sided patterned sulfonated polysulfone (sulfonation degree: 50%) prepared in example 1
FIG. 2 is a sectional electron micrograph of a heterostructure-composite proton exchange membrane prepared in example 1
FIG. 3 is a surface electron micrograph of a single-sided patterned sulfonated polysulfone (sulfonation degree: 60%) substrate prepared in example 2
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the invention is mainly designed from the following aspects: the invention discloses a technology for realizing the adjustment of micro-patterns on the surface of a proton exchange membrane matrix by changing the size of microspheres, the concentration of a polymer solution and the temperature in the process of volatilizing a solvent to solidify the matrix, and the technology is simple and easy to operate and has wide practicability on the chemical composition of the proton exchange membrane matrix (sulfonated polysulfone, sulfonated polyether ether ketone and the like). Through the design of the micro-patterns, the compatibility between the composite membranes is better, and therefore the cycle life of the fuel cell is prolonged. And secondly, preparing the composite PEM with different hydrophilic and hydrophobic heterostructure structures of the cathode and the anode. By utilizing the characteristic that the anode is easier to dehydrate and the cathode generates water, the prepared heterostructure composite PEM is an ionomer with good water absorbability close to the anode side, and the cathode is a hydrophobic ionomer. In view of the two points, the prepared heterostructure composite PEM not only has good interface compatibility, but also has higher proton conductivity and dimensional stability.
The above object of the present invention is solved by the following technical solutions:
(1) preparing a single-layer opal structure photonic crystal:
curing Polydimethylsiloxane (PDMS) in a glass culture dish as a substrate, and curing the PDMS in a polytetrafluoroethylene culture dish to obtain a removable PDMS block; and then, placing a small amount of Polystyrene (PS) microspheres on the PDMS substrate, rubbing the PDMS substrate by using another PDMS block, and self-assembling the PS microspheres on the substrate into a single-layer PS microsphere array under the action of electrostatic force.
(2) Preparation of single-side patterned proton exchange membrane substrate
Pouring a solution of a polycarbonyl ionomer on the surface of the base micro pattern; and placing the substrate with the template embedded on one side in a template remover for a certain time, and removing the template to obtain the substrate with the micro-pattern on one side.
(3) Preparation of heterostructure composite PEM
Preparing a heterostructure composite proton exchange membrane: and (3) coating POSS ionomer on one side with the micro pattern, and drying in a vacuum drying oven to obtain the heterostructure composite PEM with good interface compatibility.
As a preferred scheme, the microsphere can also be polymethyl propyleneAcid methyl ester (PMMA) or silicon dioxide (SiO)2) And (3) microspheres.
The method adopts a pouring method to transfer the single-layer opal structure photonic crystal to the surface of a single side of an ionomer on the surface of PDMS, the concentration of the ionomer for constructing the matrix is 0.15-0.5 g/ml, and the thickness of the matrix is 50-100 mu m.
The ionomer in the (2) is: one or more than two of sulfonated polysulfone (with a sulfonation degree of 20-50%) and sulfonated polyether-ether-ketone (with a sulfonation degree of 10-50%).
The temperature and time of the vacuum drying oven in the step (2) are set to be (30 ℃, 60h), (40 ℃, 48h), (50 ℃, 24h), (60 ℃, 12 h).
As a preferred option, the knife-coated ionomer may be sulfonated polysulfone (degree of sulfonation greater than 60%), sulfonated polyetheretherketone (degree of sulfonation greater than 60%), or Nafion solution.
The thickness of the water-absorbing coating obtained by blade coating is 10-50 mu m.
Example 1
(1) Preparing a single-layer opal structure photonic crystal:
curing Polydimethylsiloxane (PDMS) in a glass culture dish as a substrate, and curing the PDMS in a polytetrafluoroethylene culture dish to obtain a removable PDMS block; and then, placing a small amount of Polystyrene (PS) microspheres on the PDMS substrate, rubbing the PDMS substrate by using another PDMS block, and self-assembling the PS microspheres on the substrate into a single-layer PS microsphere array under the action of electrostatic force.
(2) Preparation of one-sided patterned sulfonated polysulfone (sulfonation degree: 50%) substrate
Pouring a DMSO solution of sulfonated polysulfone (sulfonation degree: 50%) on the micro-pattern surface of the substrate; volatilizing the solvent in a vacuum drying oven at the temperature of 40 ℃; and placing the substrate with the template embedded on one side in toluene for 1h, and removing the PS template to obtain the substrate with the micro-pattern on one side.
(3) Preparation of heterostructure composite PEM
And (3) blade-coating a solution of sulfonated POSS ionomer on one side with the micro-pattern, and placing the solution in a vacuum drying oven for drying to obtain the heterostructure composite PEM with good interface compatibility.
Table 1 shows the performance indexes of the heterostructure composite PEM prepared in embodiment 1, and it can be seen from the table that the proton conductivity of the heterostructure composite PEM is significantly better than that of the pure sulfonated polysulfone membrane at all temperatures in the fully hydrated state, and the water absorption and swelling ratios are not much different from that of the matrix.
Example 2
(1) Preparing a single-layer opal structure photonic crystal:
curing Polydimethylsiloxane (PDMS) in a glass culture dish as a substrate, and curing the PDMS in a polytetrafluoroethylene culture dish to obtain a removable PDMS block; and then, placing a small amount of Polystyrene (PS) microspheres on the PDMS substrate, rubbing the PDMS substrate by using another PDMS block, and self-assembling the PS microspheres on the substrate into a single-layer PS microsphere array under the action of electrostatic force.
(2) Preparation of one-sided patterned sulfonated polysulfone (sulfonation degree: 60%) substrate
Pouring a DMSO solution of sulfonated polysulfone (sulfonation degree: 50%) on the micro-pattern surface of the substrate; volatilizing the solvent in a vacuum drying oven at 50 ℃; and placing the substrate with the template embedded on one side in toluene for 1h, and removing the PS template to obtain the substrate with the micro-pattern on one side.
(3) Preparation of heterostructure composite PEM
A solution of sulfonated polysulfone (sulfonation: 60%) ionomer was knife-coated on the micropatterned side and dried in a vacuum oven to obtain a heterostructure composite PEM with good interfacial compatibility.
As can be seen in fig. 2, the micropattern on the matrix sulfonated polysulfone turned into a bicontinuous microstructure upon increasing temperature.
Example 3
(1) Preparing a single-layer opal structure photonic crystal:
solidifying polydimethyl in glass culture dishTaking siloxane (PDMS) as a substrate, and curing the PDMS in a culture dish made of polytetrafluoroethylene to obtain a PDMS block which can be peeled off; thereafter, a small amount of silicon dioxide (SiO) was placed on the PDMS substrate2) Microspheres, then rubbed with another PDMS block, and the SiO on the substrate under the action of electrostatic force2Microsphere self-assembly single-layer SiO2An array of microspheres.
(2) Preparation of a one-sided patterned polyetheretherketone (sulfonation degree: 50%) matrix
Pouring N, N-Dimethylformamide (DMF) solution of sulfonated polyether ether ketone (sulfonation degree: 50%) on the micro-pattern surface of the substrate; volatilizing the solvent in a vacuum drying oven at the temperature of 60 ℃; placing the substrate with the template embedded at one side in hydrofluoric acid solution for 5h, and removing SiO2And (5) template to obtain a substrate with a micro pattern on one side.
(3) Preparation of heterostructure composite PEM
Knife coating a solution of Nafion ionomer on the side with the micro-pattern, the liquid film having a thickness of about 50 μm; and placing the membrane in a vacuum drying oven for drying to obtain the heterostructure composite PEM with good interface compatibility.
Claims (5)
1. A method for preparing a heterogeneous composite proton exchange membrane by regulating and controlling an interface microstructure is characterized by comprising the following steps:
step 1, preparing a single-layer opal structure photonic crystal: placing a dry microsphere between two pieces of polydimethylsiloxane PDMS to enable the two pieces of polydimethylsiloxane PDMS to generate friction, and under the induction of the action of electrostatic force, self-assembling the microsphere on the polydimethylsiloxane PDMS substrate positioned at the bottom to form a single-layer microsphere array as a micropattern;
step 2, preparing a single-side patterned proton exchange membrane substrate: pouring a solution of a polycarbonyl ionomer on the surface of the micro pattern, placing the solution in a vacuum drying oven, placing the solution for 60 to 12 hours to volatilize a solvent until the solution is dried at the temperature of between 30 and 60 ℃, placing one side of the template embedded with the micro pattern in a template remover to remove the template, and obtaining a substrate with the micro pattern structure being a reflector crystal structure or a bicontinuous microstructure and the micro pattern on one side; the above-mentionedThe template is microsphere, the microsphere is polystyrene PS, polymethyl methacrylate PMMA or silicon dioxide SiO2Microspheres;
the concentration of the solution of the polycarbonyl ionomer is 0.1-0.5 g/ml;
step 3, preparation of the heterostructure composite proton exchange membrane: coating an ionomer with high proton conductivity on one side with the micro pattern, and drying in a vacuum drying oven to obtain a heterostructure composite PEM with good interface compatibility; the concentration of the ionomer is 0.12-0.3 g/ml.
2. The method for preparing the heterogeneous composite proton exchange membrane by regulating the interface microstructure according to claim 1, wherein the method comprises the following steps: the particle size of the microsphere is as follows: 500 nm-5 μm.
3. The method for preparing the heterogeneous composite proton exchange membrane by regulating the interface microstructure according to claim 1, wherein the method comprises the following steps: the polymer hydrocarbon-based ionomer is one or more than two of sulfonated polysulfone or sulfonated polyether ether ketone; the sulfonation degree of the sulfonated polysulfone is 20-50%; the sulfonation degree of the sulfonated polyether-ether-ketone is 10-50%.
4. The method for preparing the heterogeneous composite proton exchange membrane by regulating the interface microstructure according to claim 1, wherein the method comprises the following steps: the template remover is toluene, tetrahydrofuran or hydrofluoric acid solution.
5. The method for preparing the heterogeneous composite proton exchange membrane by regulating the interface microstructure according to claim 1, wherein the method comprises the following steps: the scraping ionomer is sulfonated POSS ionomer, sulfonated polyether-ether-ketone or Nafion solution; the sulfonation degree of the sulfonated polysulfone or the sulfonated polyether ether ketone is more than 60 percent.
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