CN106816617B - Preparation method of polymer composite electrolyte membrane - Google Patents
Preparation method of polymer composite electrolyte membrane Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
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Abstract
The invention provides a preparation method of a polymer composite electrolyte membrane, which is characterized in that a porous membrane containing a low-viscosity polymer electrolyte A solution and a high-viscosity polymer electrolyte B solution are compounded. Due to the fact that the viscosity of the solution is controlled, the polymer composite electrolyte membrane prepared by the preparation method has high filling rate and low surface roughness, so that the comprehensive performance of the polymer electrolyte is greatly improved, and the application prospect is more definite.
Description
Technical Field
The invention belongs to the field of polymer materials, and particularly relates to a preparation method of a polymer composite electrolyte membrane.
Background
The polymer electrolyte is a polymer ion conductor containing dissociable ionic groups. Because of the characteristics of good conductivity, light weight, good elasticity, easy film forming and the like of the polymer, the polymer is a hot spot for research and development of chemical power sources in recent years. At present, polymer electrolytes are mainly used in the fields of lithium ion batteries or fuel cells. In order to improve the performance such as the efficiency and the output density of the battery, it is strongly required to reduce the resistance and improve the conductivity of the polymer electrolyte membrane, and researchers have made various studies for this purpose, and there are generally two approaches as follows: (1) the method of reducing the film thickness is used for reducing the resistance of the polymer electrolyte film and increasing the power density of the cell. However, reducing the film thickness results in a reduction in the mechanical strength of the film, increasing the likelihood of damage by other components during use, and shortening the service life. (2) The conductive group in the polymer electrolyte segment is increased to improve conductivity. For a polymer electrolyte membrane used for a fuel cell, the increase of the conductive group increases the dimensional change due to the change in atmospheric humidity, decreases the durability of the membrane, and results in a reduction in the service life of the cell.
In order to solve the above problems, studies have been made to improve the strength of a polymer electrolyte membrane, reduce dimensional change, and improve durability by compounding a porous membrane with a polymer electrolyte, and various technical solutions have been proposed.
Patent document 1 proposes a composite membrane in which an ion exchange material is sufficiently impregnated in an expanded polytetrafluoroethylene (ePTFE) membrane, and the strength and dimensional stability thereof are remarkably improved. But the preparation process is complex, pores in the ePTFE can be fully filled by soaking for many times, and the smoothness of the surface of the composite membrane is not ideal due to the low viscosity of the solution.
Patent document 2 has intensively studied the influence of the pore diameter of the porous membrane on the performance of the composite membrane, and proposes a composite membrane prepared by using a porous membrane having a pore diameter in a specific range (0.3 to 5.0 μm) which can not only have excellent initial power generation characteristics but also reduce dimensional change and suppress the generation of hydrogen peroxide or the like. Although this patent suggests the beneficial effect of appropriate pore size on the performance of the composite membrane, no new composite method has been suggested.
In patent document 3, an electrolyte membrane having a first proton-conducting polymer reinforced with a nanofiber mat is proposed, which has good thermal and chemical stability when operated at a relatively high temperature and exhibits excellent dimensional stability.
Patent document 4 proposes an improved continuous coating method for producing a composite membrane, which can improve the production efficiency of the composite membrane, in order to improve the situation where acidification is likely to occur when the ePTFE is compounded with a polymer using a spraying or dipping method and the impregnation sufficiency and uniformity of the resulting composite membrane are difficult to achieve.
However, in the methods for producing a composite membrane by compounding a polymer electrolyte with a porous membrane as proposed in the above patent documents 1 to 4, the influence of the viscosity of the polymer solution on the impregnation is not clearly proposed. But in practice the situation is often encountered: when a high-viscosity solution is adopted, the surface tension of the solution is very high, and when the porous membrane is impregnated, the solution is difficult to enter the inside of a pore channel due to the fact that the capillary phenomenon of the pore channel is hindered by the too-high surface tension of the solution, so that the impregnation condition is not ideal, and the filling rate is low; when the low-viscosity solution is adopted, although the surface tension of the solution is reduced at the moment, the capillary phenomenon of a pore channel is not easy to block, and the solution is easy to impregnate into the interior of the pore channel, the solution is not easy to cover the surface of the porous membrane due to the low viscosity of the solution, so that the surface roughness of the composite membrane is increased, and the surface resistance is increased when the composite membrane is contacted with an electrode; although the above phenomenon can be improved by repeated dipping or blade coating, the preparation process becomes more complicated and the surface uniformity of the composite film is deteriorated due to multiple treatments, and it is difficult to uniformly control the entire thickness of the composite film to be 25 μm or less.
Reference to the literature
Patent document 1: WO2003/022912
Patent document 2: WO2012/046777
Patent document 3: WO2011/149732
Patent document 4: WO 2006/1-2490.
Disclosure of Invention
In order to solve the above problems, the present invention proposes a method for preparing a polymer composite electrolyte membrane, in which a porous membrane containing a low-viscosity polymer electrolyte a solution and a high-viscosity polymer electrolyte B solution are combined to obtain a polymer composite electrolyte membrane. The control of the solution viscosity can obviously improve the filling rate of the composite membrane and reduce the surface roughness, so that the comprehensive performance of the polymer electrolyte is greatly improved.
The purpose of the invention can be achieved by the following scheme:
a preparation method of a polymer composite electrolyte membrane comprises the steps of compounding a porous membrane containing a polymer electrolyte A solution with a polymer electrolyte B solution; wherein, the polymer electrolyte A and the polymer electrolyte B can be the same or different, the viscosity of the polymer electrolyte A solution at 25 ℃ is 10-99 centipoises, and the viscosity of the polymer electrolyte B solution at 25 ℃ is 100-8000 centipoises.
When the porous membrane containing the polymer electrolyte A solution is compounded with the polymer electrolyte B, a two-step process that two surfaces of the porous membrane containing the polymer electrolyte A solution are respectively compounded with the polymer electrolyte B solution is adopted: first, one surface of a porous membrane containing a polymer electrolyte A solution is combined with a polymer electrolyte B solution and dried, and then the other surface is combined with the polymer electrolyte B solution and dried. In the porous membrane containing the polymer electrolyte A solution, the content of the polymer electrolyte A solution is preferably 40% or more of the saturated liquid absorption amount of the porous membrane. When the liquid content is too low, the filling rate of the polymer composite electrolyte membrane may be affected; in order to achieve a higher filling rate, the content of the polymer electrolyte a solution in the porous membrane containing the polymer electrolyte a solution is more preferably 60% or more of the saturated liquid absorption amount of the porous membrane.
The two-step process is specifically shown in the attached figure 1: a first step of compounding and drying one surface of a porous membrane containing a polymer electrolyte A solution with a polymer electrolyte B solution; and secondly, compounding the other surface of the porous membrane with a polymer electrolyte B solution and drying to obtain the polymer composite electrolyte membrane. The method for producing the porous membrane containing the polymer electrolyte a solution of the present invention is not particularly limited, and the porous membrane can be obtained by introducing the polymer electrolyte a solution into the porous membrane by dipping, coating, or adsorption. In the above two-step process, the surface of the porous membrane containing the polymer electrolyte a solution and the polymer electrolyte B solution can be combined by conventional coating, casting, or spraying. The drying method is not particularly limited, and the drying treatment may be performed using a vacuum oven, a forced air oven, a hot plate, or the like.
The two-step process has the advantages that: (1) firstly, the porous membrane containing the polymer electrolyte A solution is obtained by filling the pore channels of the porous membrane with the low-viscosity polymer electrolyte A solution, and the surface tension of the pores in the porous membrane is sharply reduced. In this case, when the porous membrane is further combined with the polymer electrolyte B solution, the polymer electrolyte B solution can easily enter the pores of the porous membrane filled with the polymer electrolyte A solution. After the drying treatment, most of the pore channels in the porous membrane are fully filled with the polymer electrolyte A and the polymer electrolyte B, and a compact surface layer completely covered by the polymer electrolyte B is formed on the surface subjected to compounding. Without pre-filling of the low viscosity polymer electrolyte a solution, the high viscosity polymer electrolyte B would be difficult to fill inside the pore channels of the porous membrane; if only the polymer electrolyte A solution of low viscosity is pre-filled and then compounded, it is difficult to completely cover the rough surface of the porous membrane, and only a polymer composite electrolyte membrane having a high surface roughness can be obtained. In the porous membrane containing the polymer electrolyte a solution, the content of the polymer electrolyte a solution is preferably 40% or more of the saturated liquid absorption amount of the porous membrane; in order to achieve a higher filling rate, the content of the polymer electrolyte a solution in the porous membrane containing the polymer electrolyte a solution is more preferably 60% or more of the saturated liquid absorption amount of the porous membrane. In addition, the viscosity difference between the polymer electrolyte A solution and the polymer electrolyte B solution used in the step is the key point of the invention, so the viscosity of the polymer electrolyte A solution and the viscosity of the polymer electrolyte B solution at 25 ℃ are respectively 10-99 centipoise and 100-8000 centipoise, and in order to clearly distinguish the viscosity difference between the polymer electrolyte A solution and the polymer electrolyte B solution, the viscosity of the polymer electrolyte A solution and the viscosity of the polymer electrolyte B solution at 25 ℃ are preferably 20-60 centipoise and 200-8000 centipoise respectively.
After this first step, most of the pores of the porous membrane and the surface that has been compounded have been filled and covered with the polymer electrolyte. (2) In this case, the polymer electrolyte B solution is filled into the remaining small number of cell channels from the other surface of the porous membrane and forms a dense skin layer completely covered with the polymer electrolyte B on the other surface. Thus, by the production method of the present invention, a composite electrolyte membrane in which the inside of the porous membrane is completely filled and the upper and lower surfaces are completely covered with the dense polymer electrolyte layer is produced. The high packing rate contributes to a reduction in the internal resistance of the polymer composite electrolyte membrane itself and an increase in conductivity, and the low surface roughness contributes to an improvement in the contact resistance between the polymer composite electrolyte membrane and the electrode and brings about an increase in the battery performance.
In the production of the above-mentioned polymer composite electrolyte membrane, it is preferable that the polymer electrolyte A and the polymer electrolyte B used are each formed of a block copolymer comprising a segment containing an ionic group (A1) and a segment containing no ionic group (A2), and the polymer electrolyte A and the polymer electrolyte B may be the same or different, in view of the performance of the electrolyte membrane. The block copolymer may be selected from a variety of polymers, for example, a perfluoropolymer, and commercially available products such as Nafion (registered trademark) (manufactured by dupont), Flemion (registered trademark) (manufactured by asahi glass company) and Aciplex (registered trademark) (manufactured by asahi chemical company), or a polymer having an aromatic ring in the main chain and an ionic group (i.e., a non-fluorine polymer) may include polysulfone, polyethersulfone, polyphenylene ether, polyarylene ether polymer, polyphenylene sulfide, polyarylene ether ketone, polyetherketone, polyetherphosphine oxide, polybenzoxazole, polyamide, polyimide, polyetherimide, or polyimide sulfone. In view of ion conductivity and durability, the molar ratio of the segment containing an ionic group (A1) to the segment containing no ionic group (A2) in the block copolymer is preferably 0.15 to 5.0.
In view of mechanical properties, physical durability, hydrolysis resistance and cost, the segment containing an ionic group (A1) preferably contains a structural unit represented by the following formula (S1):
in the formula (S1), X1Representing a direct bond or a keto, sulfone, -PO (R)1)-、-(CF2)f1-or-C (CF)3)2-one of the above; y is1Represents one of oxygen or sulfur; r1Is an organic functional group, f1 is an integer of 1 to 5, M1Represents one of hydrogen, metal cation, ammonium ion or C1-C20 alkyl; m is an integer of 0-4, n is an integer of 0-4, and m and n are not 0 at the same time. Further considering physical durability and cost factors, in the formula (S1), X1Preferably represents a direct bond or a keto, sulfone or-C (CF)3)2-one of the above; m is preferably an integer of 0 to 2, n is preferably an integer of 0 to 2, and m and n are not 0 at the same time.
In view of mechanical properties, physical durability, hydrolysis resistance and cost, the segment (A2) containing no ionic group preferably contains a structural unit represented by the following formula (S2):
in the formula (S2), X2Representing a direct bond or a keto, sulfone, -PO (R)2)-、-(CF2)f2-or-C (CF)3)2-one of the above; y is2Represents one of oxygen or sulfur, R2Is an organic functional group, and f2 is an integer of 1 to 5.
In the polymer composite electrolyte membrane, a porous membrane can be widely used as a porous substrate for reinforcement, such as a polymer porous membrane, a porous fabric, a molecular sieve, a porous metal plate, a porous ceramic or a porous asbestos plate, wherein the polymer porous membrane can be a porous membrane made of polyolefin, polyamide, polycarbonate, cellulose, polyurethane, polyester, polyether, polyacrylate, copolyether ester, copolyether amide, polyimide or fluoropolymer. In view of strength, porosity and cost, a fluorine-containing polymer porous membrane or a polyimide porous membrane is preferable. The porous film herein may be formed by phase inversion or stretching, or may be obtained by spinning. The porosity of the porous membrane is 30-99%, and preferably 60-95% in consideration of strength and resistance; the thickness of the porous film is 1 to 25 μm, and preferably 3 to 10 μm in consideration of the strength of the resulting composite film. In further consideration of the conductivity of the entire composite membrane, it is preferable to graft or blend the porous membrane containing a conductive group.
The polymer composite electrolyte membrane prepared by the method has a completely filled section structure and smooth and compact upper and lower surfaces, the thickness of the membrane is 2-25 micrometers, the filling rate is more than 85%, and the surface roughness of the upper and lower surfaces is not higher than 0.08 mu m; the thickness is preferably 4 to 12 μm in consideration of the cell performance of the electrolyte membrane.
In addition, the introduction of the porous membrane of the polymer composite electrolyte membrane prepared by the method has no influence on the phase morphology of the polymer electrolyte, for example, the co-continuous phase morphology of the sulfonated polyether-ether-ketone can still be maintained in the sulfonated polyether-ether-ketone composite electrolyte membrane, and the maintenance of the phase morphology is favorable for maintaining the excellent conductivity of the polymer electrolyte. Meanwhile, the filling rate of the polymer composite electrolyte membrane is up to more than 85%, and the ion exchange capacity of the polymer composite electrolyte membrane is 0.8-1.1 times of that of a pure polymer electrolyte membrane, so that the conductivity of the polymer electrolyte membrane is kept, and the overall conductivity of the composite membrane is improved.
The invention provides a novel preparation method of a polymer composite electrolyte membrane, which is characterized in that a porous membrane containing a low-viscosity polymer electrolyte A solution and a high-viscosity polymer electrolyte B solution are compounded. Because the viscosity of the solution is controlled, the polymer composite electrolyte membrane with high filling rate and low surface roughness can be prepared by using a simple process, so that the comprehensive performance of the polymer electrolyte is greatly improved, and the application prospect is more definite.
Drawings
Fig. 1 is a two-step process in which both surfaces of a porous membrane containing a polymer electrolyte a solution are respectively composited with a polymer electrolyte B solution.
FIG. 2 is a scanning electron micrograph of the upper and lower surfaces of a polymer composite electrolyte membrane in which a perfluoropolymer electrolyte and an expanded polytetrafluoroethylene porous membrane were composited in example 1.
FIG. 3 is a sectional scanning electron micrograph of a polymer composite electrolyte membrane in which a perfluoropolymer electrolyte and an expanded polytetrafluoroethylene porous membrane are composited in example 1.
FIG. 4 is a sectional scanning electron micrograph of a polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte is composited with an expanded polytetrafluoroethylene porous membrane of comparative example 3.
Detailed Description
The invention is further illustrated by the following examples of preferred embodiments, which are intended to be illustrative only and not to limit the scope of the invention.
The raw materials used were:
1. polymer electrolyte:
(a) perfluoropolymer electrolyte:
nafion solution F1, commercial productCode number:
DE 520, 5% by weight solids, low fatty alcohol/water mixed solvent, viscosity at 25 ℃ of 60 cps;
nafion solution F2, trade code:
DE 2021, 20% by weight solids content, low fatty alcohol/water mixed solvent, viscosity 6000 cps at 25 ℃;
nafion solutions F1-2 were purchased from: SIGMA-Aldrich, China, Inc., as received.
(b) Non-fluoropolymer electrolyte:
sulfonated polyether ether ketone SPEEK1
Sulfonated polyether ether ketone SPEEK2
Sulfonated polyether ether ketone SPEEK3
Sulfonated polyether ether ketone SPEEK4
Sulfonated polyether ether ketone SPEEK5
Sulfonated polyether ether ketone SPEEK6
The sulfonated polyether ether ketone SPEEK 1-4 is prepared according to patent document 5(WO 2013/031675); sulfonated polyether ether ketone SPEEK 5-6 is prepared according to patent document 6(WO 2013/040985).
2. Porous membrane:
(a) expanded polytetrafluoroethylene porous membrane
Expanded polytetrafluoroethylene porous membrane PM 1: porosity of 80% and thickness of 5 μm;
expanded polytetrafluoroethylene porous membrane PM 2: the porosity is 95 percent, and the thickness is 10 mu m;
expanded polytetrafluoroethylene porous membrane PM 3: the porosity is 60 percent, and the thickness is 3 mu m;
expanded polytetrafluoroethylene porous membrane PM 4: the porosity is 90 percent, and the thickness is 15 mu m;
the expanded polytetrafluoroethylene porous membranes PM 1-4 are all purchased from: ningbo Changqi microfiltration membrane technology, Inc., for direct use.
(b) Polyimide electrospun porous membrane
Polyimide electrospun porous membrane EM 1: the porosity is 80%, and the thickness is 10 mu m;
polyimide electrospun porous membrane EM 2: porosity of 40% and thickness of 25 μm;
polyimide electrospun porous membranes EM 1-4 were purchased from: kolon, Korea, as it is. 3. Other reagents:
PET basal membrane: lumirror 125T60, east beauty, for direct use;
n-methylpyrrolidone: chemical reagents of the national drug group, Inc. can be used directly.
The measurement method of the polymer composite electrolyte membrane-related properties in the examples:
A. viscosity measurement of polymer electrolyte solution: viscometer (Brookfield DV2T USA); the polymer electrolyte solution was placed in a test cup, vacuum defoamed, and subjected to a constant temperature of 25 ℃ for 30 minutes, followed by measurement. The same sample was tested 3 times and the average was taken.
B. And (3) measuring the film thickness: potential difference meter (NIKON MF-501 Japan); and (4) after the potential difference meter is reset to zero, placing the membrane sample under the probe of the instrument for testing. 10 positions on the sample were selected for testing and then averaged.
C. And (3) measuring the surface and section appearance of the film: scanning electron microscope (JEOL JSM-6700F Japan; freezing the membrane sample in liquid nitrogen, quenching to obtain the sample photographed by the microscope, and observing on the sample stage of the microscope.
D. And (3) measuring the morphology of the membrane phase: transmission electron microscope (JEOL JEM2010 japan); the membrane sample is embedded by epoxy resin, frozen and sliced after embedding to prepare a sample, and the sample is placed on a copper platform and is placed into a transmission electron microscope for observation.
E. And (3) measuring the surface roughness: a noncontact surface roughness meter (Vertscan R5300 japan);
the membrane was placed on an observation stand, and the measurement was performed after focusing was adjusted. 3 areas on the sample were selected for testing and then averaged.
F. Determination of Filling Rate (FR) of composite membrane:
the calculation formula is as follows:
v in the above formula (Q1) is the volume occupied by the corresponding component, and is calculated from the mass and density of the component.
G. Determination of the rate of change of Size (SR):
the electrolyte membrane was cut into a square having a length of about 5cm and a width of about 5cm, the xy direction was marked (the MD/TD direction of the composite membrane was marked according to the MD/TD direction of the porous membrane), the length in the initial dry state (L) was measured with a vernier caliper after keeping the membrane constant at 25 ℃/55% RH for 12 hours0) (ii) a After the electrolyte membrane was immersed in hot water at 80 ℃ for 2 hours, the length (L) in a high-temperature wet state was measured with a vernier caliper immediately after the electrolyte membrane was taken out, and the corresponding dimensional change rate was calculated by the following formula.
The calculation formula is as follows:
dimensional change rate in X (or MD) direction:
dimensional change rate in Y (or TD) direction:
H. ion Exchange Capacity (IEC) determination:
determined by neutralization titration. The measurement was performed 3 times, and the average value was obtained.
(a) After proton substitution of the electrolyte membrane, the surface was sufficiently cleaned with pure water and wiped clean, and then vacuum-dried at 100 ℃ for 12 hours or more to obtain the dry quality of the electrolyte membrane.
(b) The electrolyte membrane was placed in 50ml of a 5 wt% sodium sulfate aqueous solution, allowed to stand for 12 hours or more, and subjected to ion exchange.
(c) Titrating the acid generated by exchange in the sodium sulfate aqueous solution by using a 0.01mol/L sodium hydroxide aqueous solution, and taking a commercial phenolphthalein/ethanol solution as an indicator and a light purple red as an end point.
(d) The formula for the calculation of ion exchange capacity is as follows:
I. proton conductivity measurement:
the electrolyte membrane is immersed in pure water at 25 ℃ for 24 hours, then placed in a constant temperature and humidity box at 80 ℃ and a relative humidity of 25-95%, kept for 30 minutes under each condition, and then the proton conductivity is measured by a constant potential alternating current impedance method.
The proton conductivity was determined by constant potential impedance measurement by a two-terminal method using an EC-Lab electrochemical measurement system as a measuring apparatus. The AC amplitude was 50 mV. The sample used a film 50mm long and 10mm wide. The measuring jig is made of phenolic resin and the measuring portion is open. Platinum plates (100 μm thick, 2 pieces) were used as electrodes, the distance between the two electrodes was 10mm, and the electrodes were disposed on both sides of the sample film, parallel to each other, and perpendicular to the longitudinal direction of the sample film.
Example 1
Polymer composite electrolyte membrane compounded by perfluor polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: nafion solution F1;
polymer electrolyte B solution: nafion solution F2;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 1.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
The porous membrane was fixed with a frame and then coated with a polymer electrolyte a solution 3 times on both surfaces, respectively, to obtain a porous membrane containing a polymer electrolyte a solution. The content of the polymer electrolyte A solution in the porous membrane was 60% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding
On one surface of the fixed porous membrane containing the polymer electrolyte a solution obtained in the step (2), a polymer electrolyte B solution was cast and dried in a vacuum oven at 60 ℃ (degree of vacuum 100Pa), and then a polymer electrolyte B solution was cast on the other surface and dried in a vacuum oven at 60 ℃ (degree of vacuum 100Pa), to obtain a polymer composite electrolyte membrane in which a perfluoropolymer electrolyte and an expanded polytetrafluoroethylene porous membrane were composited, and a transparent and uniform membrane was visually observed.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 25 microns, the filling rate is 85 percent, the surface roughness is 0.052 microns, and the IEC is 0.75 mmol/g.
When observed by using a scanning electron microscope, the upper surface and the lower surface of the polymer composite electrolyte membrane are smooth as shown in figure 2, and the section has no obvious unfilled pore channels as shown in figure 3.
The polymer composite electrolyte membrane was observed by a transmission electron microscope, and no microphase separation structure was found.
The polymer composite electrolyte membrane had a dimensional change rate of 5.3% in the MD and 4.8% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 110mS/cm and at 80 ℃ at a relative humidity of 25% at 1.9 mS/cm.
Example 2
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 50 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 10 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte A solution in the porous membrane was 100% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 100 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a 60 ℃ forced air oven. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 8 microns, the filling rate is 100%, the surface roughness is 0.070 microns, and the IEC is 1.95 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 3.5% in the MD and 4.1% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 238mS/cm and at 80 ℃ at a relative humidity of 25% at 9.4 mS/cm.
Example 3
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 2/N-methylpyrrolidone solution, having a viscosity of 99 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 3/N-methylpyrrolidone solution, having a viscosity of 8000 cps at 25 deg.C;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 3.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Fixing the porous membrane by using an outer frame, then dripping the polymer electrolyte A solution on the surface of the porous membrane, and obtaining the porous membrane containing the polymer electrolyte A solution after the solution is completely adsorbed. The content of the polymer electrolyte A solution in the porous membrane was 40% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 500 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane having the polymer electrolyte a solution adsorbed thereto to the liquid membrane and drying at 40 ℃; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried on a hot stage at 100 ℃. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 22 microns, the filling rate is 85 percent, the surface roughness is 0.041 mu m, and the IEC is 1.50 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 6.8% in the MD and 8.3% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 150mS/cm and at 80 ℃ at a relative humidity of 25% at 5.8 mS/cm.
Example 4
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 50 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 4/N-methylpyrrolidone solution with a viscosity of 2000 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 4.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 5 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte a solution in the porous membrane was 70% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 350 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a vacuum oven at 60 ℃. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 12 microns, the filling rate is 90%, the surface roughness is 0.060 mu m, and the IEC is 1.87 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 5.3% in the MD and 6.1% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at 85% relative humidity at 175mS/cm and at 80 ℃ at 25% relative humidity at 8.2 mS/cm.
Example 5
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 5/N-methylpyrrolidone solution with a viscosity of 30 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 5/N-methylpyrrolidone solution, having a viscosity of 100 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 5 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte A solution in the porous membrane was 80% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 250 micrometers is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a vacuum oven at 60 ℃. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 10 microns, the filling rate is 95%, the surface roughness is 0.070 microns, and the IEC is 2.3 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 9.0% in the MD and 8.9% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at 85% relative humidity at 420mS/cm and at 80 ℃ at 25% relative humidity at 15.0 mS/cm.
Example 6
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and polyimide electrospun porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 5/N-methylpyrrolidone solution with a viscosity of 10 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 6/N-methylpyrrolidone solution, having a viscosity of 3000 cps at 25 deg.C;
porous membrane: polyimide electrospun porous membrane EM 1.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 5 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte A solution in the porous membrane was 80% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 400 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a vacuum oven at 60 ℃. The polymer composite electrolyte membrane in which the non-fluoropolymer electrolyte and the polyimide electrospun porous membrane were composited was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 12 microns, the filling rate is 92%, the surface roughness is 0.065 mu m, and the IEC is 2.5 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 12.0% in the MD and 14.0% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at 85% relative humidity at 510mS/cm and at 80 ℃ at 25% relative humidity at 17.0 mS/cm.
Example 7
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and polyimide electrospun porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 50 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
porous membrane: polyimide electrospun porous membrane EM 2.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 10 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte a solution in the porous membrane was 90% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 100 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a vacuum oven at 60 ℃. The polymer composite electrolyte membrane in which the non-fluoropolymer electrolyte and the polyimide electrospun porous membrane were composited was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 29 microns, the filling rate is 98%, the surface roughness is 0.071 microns, and the IEC is 1.75 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure.
The polymer composite electrolyte membrane had a dimensional change rate of 3.2% in the MD and 3.5% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 210mS/cm and at 80 ℃ at a relative humidity of 25% at 7.2 mS/cm.
Comparative example 1
Perfluoro polymer electrolyte pure film
(1) Raw materials
Polymer electrolyte solution: nafion solution F2
(2) Film production
The polymer electrolyte solution was knife coated on a PET-based film to form a liquid film, which was dried in an oven at 100 ℃. A pure perfluoropolymer electrolyte membrane was obtained, which was visually observed as a transparent and uniform membrane.
(3) Performance characterization
The thickness of the perfluoropolymer electrolyte pure film is 25 micrometers, the surface roughness is 0.022 mu m, and the IEC is 0.91 mmol/g.
The upper surface and the lower surface of the pure perfluoropolymer electrolyte membrane are smooth when observed by using a scanning electron microscope.
The perfluoropolymer electrolyte pure film was observed using a transmission electron microscope, and no phase separation structure was observed.
The dimensional change rate of the perfluoropolymer electrolyte pure membrane in the x/y direction was 12.0%. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at 85% relative humidity at 129mS/cm and at 80 ℃ at 25% relative humidity at 3.8 mS/cm.
Comparative example 2
Non-fluorine polymer electrolyte pure film
(1) Raw materials
Polymer electrolyte solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
(2) film production
The polymer electrolyte solution was knife coated on a PET-based film to form a liquid film, which was dried in an oven at 100 ℃. A pure film of a non-fluoropolymer electrolyte was obtained, which was visually observed as a transparent and uniform film.
(3) Performance characterization
The thickness of the non-fluoropolymer electrolyte pure film was 20 micrometers, the surface roughness was 0.018 μm, and the IEC was 2.08 mmol/g.
The upper and lower surfaces of the pure film of the non-fluoropolymer electrolyte were smooth as observed by scanning electron microscopy.
The non-fluorine polymer electrolyte pure film is observed by a transmission electron microscope and has a co-continuous phase separation structure.
The dimensional change rate of the non-fluoropolymer electrolyte pure film in the x/y direction was 9.0%. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 240mS/cm and at 80 ℃ at a relative humidity of 25% at 10.0 mS/cm.
Comparative example 3
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Compounding
The porous film was fixed on the PET base film, and then the polymer electrolyte solution was knife-coated on the upper surface thereof and dried in an oven at 100 ℃. Then the porous membrane is torn off, the compounded side of the porous membrane is fixed on the PET basal membrane downwards, then the polymer electrolyte solution is continuously coated on the non-compounded side of the porous membrane in a scraping way and dried in an oven at 100 ℃. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and the membrane was visually observed to be translucent but many portions of the porous membrane were wrinkled.
(3) Performance characterization
The thickness of the polymer composite electrolyte membrane is 30 microns, the filling rate is 70%, the surface roughness is 0.152 mu m, and the IEC is 1.56 mmol/g.
And (3) observing by using a scanning electron microscope, wherein the upper surface and the lower surface of the polymer composite electrolyte membrane are exposed by porous membranes, and the sections of the polymer composite electrolyte membrane are provided with obvious unfilled pore channels.
The polymer composite electrolyte membrane was observed using a transmission electron microscope, and no distinct phase separation structure was observed.
The dimensional change rate of the polymer composite electrolyte membrane in the MD direction was 10.2%, and the dimensional change rate in the TD direction was 11.3%. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 150mS/cm and at 80 ℃ at a relative humidity of 25% at 2.3 mS/cm.
Comparative example 4
Raw material of polymer composite electrolyte membrane (1) compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
Polymer electrolyte solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 50 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Compounding
The polymer electrolyte solution was sprayed on both surfaces of the porous membrane, dried, and then sprayed repeatedly 5 times, dried in an oven at 100 ℃. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(3) Performance characterization
The thickness of the polymer composite electrolyte membrane is 15 microns, the filling rate is 95%, the surface roughness is 0.095 microns, and the IEC is 1.99 mmol/g.
And (3) observing by using a scanning electron microscope, wherein the upper surface and the lower surface of the polymer composite electrolyte membrane are exposed by porous membranes, but the sections have no obvious unfilled pore channels.
The polymer composite electrolyte membrane was observed using a transmission electron microscope, and no distinct phase separation structure was observed.
The dimensional change rate of the polymer composite electrolyte membrane in the MD direction was 8.3%, and the dimensional change rate in the TD direction was 7.6%. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 190mS/cm and at 80 ℃ at a relative humidity of 25% at 7.7 mS/cm.
Comparative example 5
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Compounding
The porous membrane was soaked in the polymer electrolyte solution to ensure sufficient impregnation, and then removed and rapidly dried in an oven at 100 ℃. After repeated soaking and drying for 6 times, a polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte and an expanded polytetrafluoroethylene porous membrane were compounded was obtained, and the membrane was visually observed to be transparent but uneven in thickness.
(3) Performance characterization
The thickness of the polymer composite electrolyte membrane is 35 microns, the filling rate is 85 percent, the surface roughness is 0.092 mu m, and the IEC is 1.92 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and obviously unfilled pores on the cross section by observing through a scanning electron microscope.
The polymer composite electrolyte membrane was observed using a transmission electron microscope, and no distinct phase separation structure was observed.
The dimensional change rate of the polymer composite electrolyte membrane in the MD direction was 7.5%, and the dimensional change rate in the TD direction was 7.2%. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at a relative humidity of 85% at 210mS/cm and at 80 ℃ at a relative humidity of 25% at 5.2 mS/cm.
Comparative example 6
Polymer composite electrolyte membrane compounded by non-fluorine polymer electrolyte and expanded polytetrafluoroethylene porous membrane
(1) Raw materials
Polymer electrolyte a solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 150 centipoise at 25 ℃;
polymer electrolyte B solution: sulfonated polyetheretherketone SPEEK 1/N-methylpyrrolidone solution with a viscosity of 1000 centipoise at 25 ℃;
porous membrane: an expanded polytetrafluoroethylene porous membrane PM 2.
(2) Preparation of porous Membrane containing Polymer electrolyte A solution
Immersing the porous membrane into the polymer electrolyte A solution, standing for 10 minutes, taking out and fixing by using an outer frame to obtain the porous membrane containing the polymer electrolyte A solution. The content of the polymer electrolyte A solution in the porous membrane was 100% of the saturated liquid absorption amount of the porous membrane.
(3) Compounding:
firstly, a scraper with the thickness of 100-500 microns is used for scraping and coating a polymer electrolyte B solution on a PET base film to form a liquid film; attaching one surface of the porous membrane adsorbed with the polymer electrolyte a solution to the liquid film and drying at room temperature; then, the polymer electrolyte B solution was further cast into a film directly on the other surface of the porous film and dried in a 60 ℃ forced air oven. A polymer composite electrolyte membrane in which a non-fluoropolymer electrolyte was composited with an expanded polytetrafluoroethylene porous membrane was obtained, and was visually observed as a transparent and uniform membrane.
(4) Performance characterization
The thickness of the polymer composite electrolyte membrane is 15 microns, the filling rate is 70%, the surface roughness is 0.082 mu m, and the IEC is 1.52 mmol/g.
The polymer composite electrolyte membrane has smooth upper and lower surfaces and no obvious unfilled pore channel in the cross section by using a scanning electron microscope for observation.
The polymer composite electrolyte membrane is observed by using a transmission electron microscope and has a co-continuous phase separation structure. The polymer composite electrolyte membrane had a dimensional change rate of 10.1% in the MD and 12.3% in the TD, and was excellent in water resistance. The proton conductivity was measured using an electrochemical workstation at 80 ℃ at 85% relative humidity at 15.3mS/cm and at 80 ℃ at 25% relative humidity at 0.02 mS/cm.
Claims (9)
1. A preparation method of a polymer composite electrolyte membrane is characterized by comprising the following processes: compounding a porous membrane containing a polymer electrolyte A solution and having a content of 40% or more of the saturated liquid absorption amount with a polymer electrolyte B solution; wherein, the polymer electrolyte A and the polymer electrolyte B can be the same or different, the viscosity of the polymer electrolyte A solution at 25 ℃ is 10-99 centipoises, and the viscosity of the polymer electrolyte B solution at 25 ℃ is 100-8000 centipoises.
2. The method of producing a polymer composite electrolyte membrane according to claim 1, characterized in that: when the porous membrane containing the polymer electrolyte A solution is compounded with the polymer electrolyte B solution, a two-step process of compounding two surfaces of the porous membrane containing the polymer electrolyte A solution with the polymer electrolyte B solution is adopted: first, one surface of a porous membrane containing a polymer electrolyte A solution is combined with a polymer electrolyte B solution and dried, and then the other surface is combined with the polymer electrolyte B solution and dried.
3. The method for producing a polymer composite electrolyte membrane according to claim 1, characterized in that: the polymer electrolyte a and the polymer electrolyte B are each formed of a block copolymer including a segment a1 containing an ionic group and a segment a2 containing no ionic group.
4. The method for producing a polymer composite electrolyte membrane according to claim 3, characterized in that: the molar ratio of the chain segment A1 containing the ionic group to the chain segment A2 containing no ionic group is 0.15-5.0.
5. The method of producing a polymer composite electrolyte membrane according to claim 3, characterized in that: the segment a1 containing an ionic group contains a structural unit represented by the following formula S1:
in the formula S1, X1Representing a direct bond or a keto, sulfone, -PO (R)1)-、-(CF2)f1-, or-C (CF)3)2-one of the above; y is1Represents one of oxygen or sulfur; r1Is an organic functional group, f1 is an integer of 1 to 5, M1Represents one of hydrogen, metal cation, ammonium ion or C1-C20 alkyl; m is an integer of 0-4, n is an integer of 0-4, and m and n are not 0 at the same time.
6. The method of producing a polymer composite electrolyte membrane according to claim 5, characterized in that: in the formula S1, X1Represents a direct bond or a keto group, sulfone group or-C (CF)3)2-one of the above; m is an integer of 0-2, n is an integer of 0-2, and m and n are not 0 at the same time.
7. The method of producing a polymer composite electrolyte membrane according to claim 3, characterized in that: the segment A2 containing no ionic group contains a structural unit represented by the following formula S2:
in the formula S2, X2Representing a direct bond or a keto, sulfone, -PO (R)2)-、-(CF2)f2-, or-C (CF)3)2-one of the above; y is2Represents one of oxygen or sulfur, R2Is an organic functional group, and f2 is an integer of 1 to 5.
8. The method of producing a polymer composite electrolyte membrane according to claim 1, characterized in that: the porous membrane is a fluoropolymer porous membrane or a polyimide porous membrane.
9. The method of producing a polymer composite electrolyte membrane according to claim 1, characterized in that: the thickness of the polymer composite electrolyte membrane is 2-25 micrometers, the filling rate is more than 85%, and the surface roughness of the upper surface and the surface roughness of the lower surface are both not higher than 0.08 mu m.
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| CN103814062A (en) * | 2011-09-20 | 2014-05-21 | 东丽先端材料研究开发（中国）有限公司 | Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using same |
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