CN110504474A - 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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- CN110504474A CN110504474A CN201910787420.1A CN201910787420A CN110504474A CN 110504474 A CN110504474 A CN 110504474A CN 201910787420 A CN201910787420 A CN 201910787420A CN 110504474 A CN110504474 A CN 110504474A
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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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- 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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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 proton exchange membrane fields, are related to a kind of regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane
Method, use surface micro-patterning handle sulfonated polysulfone membrane for matrix, its surface blade coating sulfonation POSS ionomer or
Nafion solution, to obtain the heterojunction structure compound proton exchange membrane that preparation has good interface compatibility.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) is usually by bipolar plates, gas diffusion layers, catalyst layer and proton exchange
Film (PEM) is constituted.Wherein, PEM is one of core component of PEMFC, needs higher chemical and thermal stability, good machine
Tool performance, higher proton conductivity and lower fuel permeability etc. are to meet application requirement.
The anode of fuel cell is typically chosen the H for being passed through humidification2As fuel, oxidation loses electricity under the effect of the catalyst
The H that son obtains+It is transmitted to cathode through PEM, O occurs for the electronics for being transmitted to cathode with oxygen and external circuit2Reduction, generate water.By
This anode that can be seen that fuel cell needs water to guarantee the transmission of proton in PEM, and cathode is then needed to be discharged in time and be produced
Raw water, therefore, PEM should be designed to the heterojunction structure film that anode-side is hydrophilic and cathode side is hydrophobic；But current commercialized PEM is still
For homogeneous membrane.
Currently, being widely applied in PEMFC by the perfluorinated sulfonic acid PEM of representative of Nafion, but the price of perfluoro sulfonic acid membrane
Expensive and fuel leak rate is high.In recent years to solve the above-mentioned problems, researcher has studied with higher glass transition temperature
(Tg) and chemical stability hydrocarbon based polyalcohol, such as: polysulfones (PSF), polybenzimidazoles (PBI), polyimides (PI) or
Person's polyether-ether-ketone (PEEK) etc..But these polymer must carry out sulfonation or it is phosphate-doped could be used as PEM, due to function base
The introducing of group, there are Trade-off effects with proton conductivity for mechanical performance.Therefore, for balancing machine performance and proton
The relationship of conductivity, researcher are prepared for the various hydridization PEM based on hydrocarbon-based.
Composite algorithm is the method for simple and efficient modified commercialization film preparation MULTILAYER COMPOSITE PEM a kind of.The advantage of this method
It is that the asymmetric membrane with heterogeneous heterojunction structure structure can be prepared, in differential salt concentration cell, vanadium fluid cell and proton exchange
There is huge application prospect in membrane cell.And it is this there are the compound of weak interface interaction force, there are interface impedances greatly,
Caducous problem influences PEMFC in the output and long-term cycle life of high power density.Based on this, Hee-Tak Kim et al.
(Adv.Mater.2017,29,1603056) three-dimensional interlocking perfluorinated sulfonic acid/polysulfones/perfluor sulphur is prepared for by template removal method
The compound PEM of acid has found that the composite membrane of preparation has low impedance and good cyclical stability after tested.But how to make on a large scale
The standby compound PEM of heterojunction structure with good interface compatibility is still a problem to be solved.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of regulation interface microstructure preparation Heterogeneous Composite matter
The method of proton exchange, solve proton exchange membrane anode and cathode caused because of the difference of response characteristic PEM proton conductivity decline and
The problem of swelling ratio increases.
Technical solution
A method of regulation interface microstructure prepares Heterogeneous Composite proton exchange membrane, it is characterised in that steps are as follows:
The preparation of step 1, single layer photonic crystal of opals structure: it is placed between two pieces of polydimethylsiloxanes dry
Dry microballoon makes two pieces of polydimethylsiloxanes generate friction, and microballoon is being located at bottom under the effect induction of electrostatic force
It is micro- pattern that single layer micro-sphere array is self-assembly of in the polydimethylsiloxane substrate in portion；
The preparation of step 2, unilateral patterning proton exchange membrane matrix: poly- hydrocarbon-based ionomer is poured in micro- pattern plane
Solution is placed in a vacuum drying oven, and under the conditions of 30 DEG C~60 DEG C of temperature, places 60h~12h solvent flashing to drying, by mould
Embedding micro- pattern side, which is placed in template remover, in plate removes template, and obtaining micropatterning is inverse photonic crystals structure or double
The unilateral side of continuous micro-structure has the matrix of micro- pattern；
The concentration of the solution of the poly- hydrocarbon-based ionomer is 0.1~0.5g/ml；
The preparation of step 3, heterojunction structure compound proton exchange membrane: high proton conductivity is scratched in the side with micro- pattern
Ionomer, place in a vacuum drying oven dry after obtain that there is the compound PEM of the heterojunction structure of good interface compatibility；It is described
The concentration of ionomer is 0.12~0.3g/ml.
The microballoon are as follows: polystyrene PS, polymetylmethacrylate or silica SiO2Microballoon.
The microspherulite diameter are as follows: 500nm~5 μm.
The poly- hydrocarbon-based ionomer is one or more of sulfonated polysulfone or sulfonated polyether-ether-ketone；The sulfonation
The sulfonation degree of polysulfones 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 ionomer of the blade coating be sulfonation POSS ionomer, sulfonated polyether-ether-ketone or Nafion solution；The sulfonation is poly-
The sulfonation degree of sulfone or sulfonated polyether-ether-ketone is greater than 60%.
Beneficial effect
A kind of method of regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane proposed by the present invention, is turned by template
Move the matrix for preparing unilateral micro-patterning；Then, template is removed to get the base regulatable to micro- pattern using template remover
Body.Second step obtains excellent different of interface binding power in the ionomer with micro- patterned side blade coating high proton conductivity after dry
Matter heterojunction structure structure composite proton exchange membrane.The compound PEM of heterojunction structure prepared by the present invention is under full hydrated test mode
Proton conductivity has an apparent rising, its proton conductivity improves nearly 1.1 times, and the side of preparation compared to pure matrix at 80 DEG C
Method is simple, widely applicable, is conducive to commercially produce on a large scale.
The present invention is directed to the different characteristics of PEMFC anode and cathode, and the compound PEM of heterojunction structure is that water imbibition is preferable close to anode-side
Ionomer, and cathode surveys the poly- hydrocarbon-based ionomer low using more hydrophobic, good mechanical stability, fuel permeability, and
By the micro-patterning of design interface, make the compound PEM of heterojunction structure that there is good interface compatibility.
The present invention has had the following advantages compared with current material and technology:
1) it can be enhanced using the compound PEM of heterojunction structure made of preparation method proposed by the invention in anode and cathode
Adaptability under different reaction conditions；
2) proton conductivity under full hydrated test mode of compound PEM prepared by the present invention has an apparent rising, and 80
DEG C when its proton conductivity compared to pure sulfonated polysulfone matrix improve nearly 1.1 times；
3) preparation method of the present invention is simple, can carry out post-processing modification to existing commercialization film, is conducive to extensive
Commercially produce.
Detailed description of the invention
Fig. 1 is that embodiment 1 prepares unilateral patterning sulfonated polysulfone (sulfonation degree: 50%) the surface electromicroscopic photograph of matrix
Fig. 2 is the section electromicroscopic photograph that embodiment 1 prepares heterojunction structure compound proton exchange membrane
Fig. 3 is that embodiment 2 prepares unilateral patterning sulfonated polysulfone (sulfonation degree: 60%) the surface electromicroscopic photograph of matrix
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
The present invention is mainly designed from such as lower angle: one, having been invented a kind of molten by changing microballoon size, polymer
The concentration of liquid and temperature during solvent flashing cured matrix realize that the micro- pattern of proton exchange membrane matrix surface is adjustable
Technology, this is technically simple easy to operate, and wide (sulfonated polysulfone, sulfonation are poly- to the chemical composition practicability of proton exchange membrane matrix
Ether ether ketone etc.).By the design of micro- pattern, keep the compatibility between composite membrane more preferable, to promote the circulation longevity of fuel cell
Life.Two, it is prepared for anode and cathode difference hydrophilic and hydrophobic heterojunction structure structure composite PEM.Using anode more dehydration, cathode is generated
The characteristics of water, the compound PEM of the heterojunction structure of preparation is the ionomer of good water absorption close to anode-side, and cathode is then more hydrophobic
Ionomer.In view of the above two o'clock, the compound PEM of the heterojunction structure of preparation not only has a good interface compatibility, also have compared with
High proton conductivity and dimensional stability.
Above-mentioned purpose of the invention, which adopts the following technical scheme that, to be resolved:
(1) preparation of single layer photonic crystal of opals structure:
Solidify dimethyl silicone polymer (PDMS) in glass culture dish and be used as substrate, and in the culture dish of polytetrafluoroethylene (PTFE)
The middle PDMS that solidifies has obtained one piece of PDMS block that can be peeled；Later, a small amount of polystyrene is placed in PDMS substrate
(PS) microballoon, later with another PDMS block friction, PS microballoon under the action of electrostatic force in substrate is self-assembled into list
Layer PS micro-sphere array.
(2) preparation of unilateral patterning proton exchange membrane matrix
The solution of poly- hydrocarbon-based ionomer is poured in the micro- pattern plane of above-mentioned matrix；Different temperatures item in a vacuum drying oven
Different time solvent flashing is placed under part to drying, and side is placed on certain time in template remover embedded with the matrix of template
After remove template, obtain the unilateral matrix with micro- pattern.
(3) preparation of the compound PEM of heterojunction structure
The preparation of heterojunction structure compound proton exchange membrane: POSS ionomer is scratched in the side with micro- pattern, is placed in
Obtain that there is the compound PEM of the heterojunction structure of good interface compatibility after drying in vacuum oven.
As a preferred embodiment, microballoon may be polymethyl methacrylate (PMMA) or silica (SiO2) micro-
Ball.
Single layer photonic crystal of opals structure is transferred to the table of ionomer unilateral side using casting method by this hair on the surface PDMS
Face, construct the ionomer of matrix concentration be 0.15~0.5g/ml, matrix with a thickness of 50-100 μm.
In (2) from polymer are as follows: sulfonated polysulfone (sulfonation degree be 20%~50%), sulfonated polyether-ether-ketone (sulfonation
One or more of degree is 10%~50%).
The temperature and time of vacuum oven is set as (30 DEG C, 60h) in (2), (40 DEG C, 48h), (50 DEG C,
For 24 hours), (60 DEG C, 12h).
As a preferred embodiment, the ionomer of blade coating can be sulfonated polysulfone (sulfonation degree is greater than 60%), sulfonated polyether
Ether ketone (sulfonation degree is greater than 60%) or Nafion solution.
The coating of drafting that the present invention scratches is with a thickness of 10-50 μm.
Embodiment 1
(1) preparation of single layer photonic crystal of opals structure:
Solidify dimethyl silicone polymer (PDMS) in glass culture dish and be used as substrate, and in the culture dish of polytetrafluoroethylene (PTFE)
The middle PDMS that solidifies has obtained one piece of PDMS block that can be peeled；Later, a small amount of polystyrene is placed in PDMS substrate
(PS) microballoon, later with another PDMS block friction, PS microballoon under the action of electrostatic force in substrate is self-assembled into list
Layer PS micro-sphere array.
(2) unilateral patterning sulfonated polysulfone (sulfonation degree: the 50%) preparation of matrix
Sulfonated polysulfone (sulfonation degree: DMSO solution 50%) is poured in the micro- pattern plane of above-mentioned substrate；In vacuum oven
In solvent flashing, temperature setting be 40 DEG C；Side is placed in toluene after placement 1h embedded with the matrix of template and removes PS mould
Plate obtains the unilateral matrix with micro- pattern.
(3) preparation of the compound PEM of heterojunction structure
In the solution of the side blade coating sulfonation POSS ionomer with micro- pattern, places and obtained after drying in a vacuum drying oven
To the compound PEM of heterojunction structure with good interface compatibility.
Table 1 is the performance indicator that case study on implementation 1 prepares the compound PEM of resulting heterojunction structure, as can be seen from the table, complete
Under hydration status, the proton conductivity of the compound PEM of heterojunction structure is all substantially better than pure sulfonated polysulfone membrane at various temperatures, and inhales
Water rate is not much different with swelling ratio and matrix.
Embodiment 2
(1) preparation of single layer photonic crystal of opals structure:
Solidify dimethyl silicone polymer (PDMS) in glass culture dish and be used as substrate, and in the culture dish of polytetrafluoroethylene (PTFE)
The middle PDMS that solidifies has obtained one piece of PDMS block that can be peeled；Later, a small amount of polystyrene is placed in PDMS substrate
(PS) microballoon, later with another PDMS block friction, PS microballoon under the action of electrostatic force in substrate is self-assembled into list
Layer PS micro-sphere array.
(2) unilateral patterning sulfonated polysulfone (sulfonation degree: the 60%) preparation of matrix
Sulfonated polysulfone (sulfonation degree: DMSO solution 50%) is poured in the micro- pattern plane of above-mentioned substrate；In vacuum oven
In solvent flashing, temperature setting be 50 DEG C；Side is placed in toluene after placement 1h embedded with the matrix of template and removes PS mould
Plate obtains the unilateral matrix with micro- pattern.
(3) preparation of the compound PEM of heterojunction structure
In the side blade coating sulfonated polysulfone with micro- pattern, (sulfonation degree: it is dry to be placed in vacuum for the 60%) solution of ionomer
Obtain that there is the compound PEM of the heterojunction structure of good interface compatibility after drying in dry case.
From in attached drawing 2 as can be seen that micro- pattern transition continuous micro-structure in pairs in matrix sulfonated polysulfone after increasing temperature.
Embodiment 3
(1) preparation of single layer photonic crystal of opals structure:
Solidify dimethyl silicone polymer (PDMS) in glass culture dish and be used as substrate, and in the culture dish of polytetrafluoroethylene (PTFE)
The middle PDMS that solidifies has obtained one piece of PDMS block that can be peeled；Later, a small amount of silica is placed in PDMS substrate
(SiO2) microballoon, the SiO later with another PDMS block friction, under the action of electrostatic force in substrate2Microballoon is self-assembled into
Single layer SiO2Micro-sphere array.
(2) unilateral patterning polyether-ether-ketone (sulfonation degree: the 50%) preparation of matrix
Sulfonated polyether-ether-ketone (sulfonation degree: N,N-dimethylformamide 50%) is poured in the micro- pattern plane of above-mentioned substrate
(DMF) solution；The solvent flashing in vacuum oven, temperature setting are 60 DEG C；Side is placed on embedded with the matrix of template
SiO is removed after placing 5h in hydrofluoric acid solution2Template obtains the unilateral matrix with micro- pattern.
(3) preparation of the compound PEM of heterojunction structure
With micro- pattern side blade coating Nafion ionomer solution, about 50 μm of thickness of liquid film；It is dry to be placed in vacuum
Obtain that there is the compound PEM of the heterojunction structure of good interface compatibility after drying in dry case.
Claims (6)
1. a kind of method of regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane, it is characterised in that steps are as follows:
The preparation of step 1, single layer photonic crystal of opals structure: it is micro- that drying is placed between two pieces of polydimethylsiloxanes
Ball makes two pieces of polydimethylsiloxanes generate friction, and microballoon is being located at bottom under the effect induction of electrostatic force
It is micro- pattern that single layer micro-sphere array is self-assembly of in polydimethylsiloxane substrate；
The preparation of step 2, unilateral patterning proton exchange membrane matrix: the molten of poly- hydrocarbon-based ionomer is poured in micro- pattern plane
Liquid is placed in a vacuum drying oven, and under the conditions of 30 DEG C~60 DEG C of temperature, places 60h~12h solvent flashing to drying, by template
In embedding micro- pattern side be placed in template remover and remove template, obtaining micropatterning is inverse photonic crystals structure or doubly-linked
The unilateral side of continuous micro-structure has the matrix of micro- pattern；
The concentration of the solution of the poly- hydrocarbon-based ionomer is 0.1~0.5g/ml；
The preparation of step 3, heterojunction structure compound proton exchange membrane: with micro- pattern side blade coating high proton conductivity from
Polymers is placed and obtains having the compound PEM of the heterojunction structure of good interface compatibility after drying in a vacuum drying oven；It is described from poly-
The concentration of object is 0.12~0.3g/ml.
2. the method for regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane according to claim 1, it is characterised in that:
The microballoon are as follows: polystyrene PS, polymetylmethacrylate or silica SiO2Microballoon.
3. the method for regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane according to claim 1, it is characterised in that:
The microspherulite diameter are as follows: 500nm~5 μm.
4. the method for regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane according to claim 1, it is characterised in that:
The poly- hydrocarbon-based ionomer is one or more of sulfonated polysulfone or sulfonated polyether-ether-ketone；The sulphur of the sulfonated polysulfone
Change degree is 20%~50%；The sulfonation degree of the sulfonated polyether-ether-ketone is 10%~50%.
5. the method for regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane according to claim 1, it is characterised in that:
The template remover is toluene, tetrahydrofuran or hydrofluoric acid solution.
6. the method for regulation interface microstructure preparation Heterogeneous Composite proton exchange membrane according to claim 1, it is characterised in that:
The ionomer of the blade coating is sulfonation POSS ionomer, sulfonated polyether-ether-ketone or Nafion solution；The sulfonated polysulfone or sulfonation
The sulfonation degree of polyether-ether-ketone is greater than 60%.
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| CN111799491A (en) * | 2020-07-29 | 2020-10-20 | 江苏大学 | Fuel cell proton exchange membrane based on concave-convex composite microstructure |
| CN111864244A (en) * | 2020-07-29 | 2020-10-30 | 江苏大学 | Fuel cell proton exchange membrane with microtexture and processing method thereof |
| CN114597460A (en) * | 2022-01-17 | 2022-06-07 | 北京化工大学 | Preparation of integrated membrane electrode for reducing interface impedance |
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