CN111864243B - Preparation method and application of composite alkaline polymer electrolyte membrane - Google Patents

Preparation method and application of composite alkaline polymer electrolyte membrane Download PDF

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CN111864243B
CN111864243B CN201910340713.5A CN201910340713A CN111864243B CN 111864243 B CN111864243 B CN 111864243B CN 201910340713 A CN201910340713 A CN 201910340713A CN 111864243 B CN111864243 B CN 111864243B
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polymer electrolyte
electrolyte membrane
fiber porous
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membrane layer
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CN111864243A (en
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宋微
杨跃
高学强
邵志刚
俞红梅
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Dalian Institute of Chemical Physics of CAS
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a preparation method and application of a composite alkaline polymer electrolyte membrane. The composite alkaline polymer electrolyte membrane is characterized by comprising an asymmetric structure of a compact membrane layer and a fiber porous membrane layer, wherein the compact membrane layer is prepared by using a tape casting method, and the fiber porous membrane layer is prepared by using a high-voltage electrostatic spinning method. Compared with the prior art, the composite alkaline polymer electrolyte membrane has good ion and water transfer characteristics, shows high ionic conductivity, and shows good performance when applied to an alkaline fuel cell (779 mW/cm at 60℃)2)。

Description

Preparation method and application of composite alkaline polymer electrolyte membrane
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a composite alkaline polymer electrolyte membrane.
Background
The fuel cell is a device capable of directly converting chemical energy in reactants into electric energy through electrochemical reaction, has the characteristics of high energy conversion efficiency, low noise and environmental friendliness, and has huge application prospects in the fields of fixed power stations, vehicle power systems, portable power supplies and the like. Compared with an acidic Proton Exchange Membrane Fuel Cell (PEMFC), an alkaline membrane fuel cell (AEMFC) has the advantages of fast reaction of oxygen reduction kinetics, small corrosion to metal plates, small demand for noble metals, low cost of counterfeiting and the like, and is gradually the focus of research attention of fuel cells.
An alkaline polymer electrolyte membrane (AEM) is used as one of the core components of an AEMFC, and needs to simultaneously meet the requirements of blocking anode and cathode gases, good capability of conducting hydroxide ions, high strength, good size and alkali stability and the like. It was reported as early as 2011 in Journal of Membrane Science, 377, 2011, 1-35 that commercial cross-linked polystyrene based AEM and its aminated derivatives in blends with other polymers are not very stable in electrochemical or alkaline environments. Vijayaleks Vijayakumar et al in Journal of Industrial and Engineering Chemistry, 70, 2019, 70-86, state that many researchers are now focusing on the synthesis of polymeric basic anion exchange membranes with high ionic conductivity and excellent chemical stability, as well as new electrocatalysts that favor low cost. Polymers having a main chain structure such as polyetherimide, polyphenylene ether, polybenzimidazole, polyarylethersulfone, polyetherketone and different polymeric ionic liquids have been widely used for preparing anion exchange membranes by introducing various hydroxide conducting groups such as quaternary ammonium groups, imidazole groups, guanidino groups and the like for modification. However, particularly those membranes having a higher content of ionic groups exhibit high swelling properties, and mechanical and electrochemical properties will be deteriorated under high humidity and high temperature. It is also noted that by using block copolymers, crosslinking, blending and using nanocomposite membranes, the membranes can be adaptively resistant to swelling and improve the performance of the membranes.
The high-voltage electrostatic spinning is used as a novel material preparation means, a high-molecular polymer solution is charged under the condition of high voltage static electricity and is converted into polymer nano fibers with the diameter of hundreds of nanometers to 1 micrometer under the action of an electric field force, the polymer fibers obtained by the method have the special properties of nano size effect, large specific surface area, orientation of polymer chains along fiber chains and the like, and have great prospects in the fields of nano catalysis, filtration, biomedical treatment and the like. Xue Gong et al, International journal of hydrogenetic energy, 43, 2018, 21547-21559, noted that electrospun formed fibrous membranes can exhibit superior conductivity (1.7 times that of cast membranes) with a greater increase in mass transfer within the membrane.
The patent of application No. 201611146481.2 discloses a composite alkaline polymer electrolyte membrane, which is characterized in that an alkaline polymer fiber porous membrane is obtained by utilizing an electrostatic spinning technology, and then the alkaline polymer electrolyte membrane is prepared by adopting a hot pressing or solvent soaking method. However, the hot pressing method adopted by the technology can not make the fiber membrane compact and can not meet the requirement of blocking cathode and anode gases, and the solvent soaking method can also damage the fiber structure and can not utilize the orientation of the polymer chain along the fiber chain to enhance the characteristic of hydroxyl transmission.
Disclosure of Invention
The invention aims to provide a composite alkaline polymer electrolyte membrane and a preparation method and application thereof. The composite alkaline polymer electrolyte membrane has good capability of blocking negative and positive gases, good ion and water transfer characteristics, high ionic conductivity and good performance (60 ℃, 779 mW/cm) when being applied to an alkaline fuel cell2)。
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the invention provides a composite alkaline polymer electrolyte membrane on one hand, which comprises the following preparation steps: (1) the composite membrane is characterized by comprising (1) an asymmetric composite membrane layer formed by n layers of compact membrane layers and m layers of fiber porous membrane layers, wherein the asymmetric composite membrane layer is mutually crossly stacked, (2) the composite membrane layer is subjected to ammonification and alkali exchange to obtain the composite alkaline polymer electrolyte membrane; the compact film layer is prepared by a casting method of a block polymer subjected to chloromethylation; the fiber porous membrane layer is prepared by a block polymer subjected to chloromethylation through an electrostatic spinning technology; the block polymer is a diblock or triblock polymer containing a styrene block; n is more than or equal to 1, m is more than or equal to 1, and n and m are integers; the dense film layer and the fiber porous film layer are crossly stacked, and n is m or n is m +1 or m is n + 1; the porosity of the compact film layer is less than 0.1%; the porosity of the fiber porous membrane layer is 10-80%.
Based on the technical scheme, preferably, the thickness of the compact film layer is 1-200 um; the thickness of the fiber porous membrane layer is 1-200um, and the diameter of the fiber is 0.1-5 um.
The compact film layer is prepared by a tape casting method, and the fiber porous film layer is prepared by a high-voltage electrostatic spinning method. Both the dense membrane layer and the fibrous porous membrane layer contain one or more anion-conducting resin precursors.
The invention also provides a preparation method of the composite alkaline polymer electrolyte membrane, which comprises the following steps: the preparation method comprises the steps of forming an anion-conducting resin precursor by using a block polymer through a chloromethylation reaction, forming a compact membrane layer and a fiber porous membrane layer by independently or continuously utilizing a template casting and high-voltage electrostatic spinning method by utilizing the anion-conducting resin precursor, and combining the compact membrane layer and the fiber porous membrane layer to form a composite alkaline polymer electrolyte membrane precursor. And aminating the precursor of the composite alkaline polymer electrolyte membrane, and further performing alkali exchange to obtain the composite alkaline polymer electrolyte membrane. The method comprises the following specific steps:
(1) dissolving a block polymer in a solvent A, preparing a block polymer solution, stirring at room temperature for more than 12 hours until the block polymer solution is completely dissolved, then sequentially adding a chloromethylation reagent and a catalyst into the block polymer solution, keeping the temperature at 40-80 ℃, stirring for reaction for 4-12 hours, pouring the solution obtained after the reaction into a solvent B to separate out white flocculent resin, separating, washing and drying to obtain an anion-conductive resin precursor; the mass ratio of the block polymer to the solvent A to the catalyst to the chloromethylation reagent is 1 (20-100) to (1-5) to (2-10); the addition amount of the solvent B is enough and is about 50 to 200 times of the amount of the precipitate;
(2) dissolving the anion-conducting resin precursor obtained in the step (1) in a solvent C, stirring at 10-60 ℃ for 0.1-24h to obtain compact film layer resin slurry, uniformly pouring the compact film layer resin slurry into a flat plate type mould, putting the flat plate type mould into a drying box at 25-100 ℃, keeping for 6-48h, and evaporating the solvent to obtain a compact film layer of the composite alkaline polymer electrolyte film precursor; the mass ratio of the anion-conducting resin precursor to the solvent C is 1: 5-100;
(3) dissolving the anion-conductive resin precursor obtained in the step (1) in a solvent D, stirring at 10-60 ℃ for 10min-24h to obtain fiber porous membrane layer resin slurry, a: filling the fiber porous membrane layer resin slurry into an injection device with a needle head, fixing the injection device on a support of a high-voltage electrostatic spinning machine, spinning the fiber porous membrane layer resin slurry on a collector in the shape of a flat plate or a roller and the like by using a high-voltage electrostatic spinning technology and using high voltage of 1-30kV, collecting the collector, taking an aluminum foil as a substrate, placing the compact membrane layer obtained in the step (2) on the substrate, and spinning the fiber porous membrane layer resin slurry on one side of the compact membrane layer obtained in the step (2) by using an electrostatic spinning technology to obtain a composite alkaline polymer electrolyte membrane precursor; b: pouring the fiber porous membrane layer resin slurry into an injection device with a needle head, fixing the injection device on a bracket of a high-voltage electrostatic spinning machine, spinning the fiber porous membrane layer resin slurry on a collector in the shape of a flat plate or a roller and the like by using a high-voltage electrostatic spinning technology and high voltage of 1-30kV to obtain a fiber porous membrane layer of a composite alkaline polymer electrolyte membrane precursor; carrying out hot pressing, surface coating or pouring immersion on the fiber porous membrane layer and the compact membrane layer obtained in the step (2) to obtain a precursor of the composite alkaline polymer electrolyte membrane; the mass ratio of the anion-conducting resin precursor to the solvent D is 1: 5-100;
in the step, the composite alkaline polymer electrolyte membrane precursor can be obtained through two modes, wherein one mode is that the compact membrane layer and the fiber porous membrane layer are respectively manufactured, and the compact membrane layer and the fiber porous membrane layer are combined by hot pressing or a solvent coating surface or pouring immersion mode to form two layers or more than two layers of composite alkaline polymer electrolyte membrane precursors. The other method is that firstly, a compact film layer is manufactured, the compact film layer is fixed on a flat plate or a roller type collector of a high-voltage electrostatic spinning machine, and then the fiber porous film layer is directly spun on the compact film layer according to the method for manufacturing the fiber porous film layer to form a composite alkaline polymer electrolyte film precursor with two or more layers;
(4) soaking the precursor of the composite alkaline polymer electrolyte membrane obtained in the step (3) in an ammonium solution for further ammonification (functionalization), taking out after soaking for 24-48h at 25-60 ℃, and washing with deionized water for more than 2 times to obtain an ammonified precursor of the composite alkaline polymer electrolyte membrane; the addition amount of the ammonium solution is enough to immerse the precursor of the composite alkaline polymer electrolyte membrane; the concentration of the ammoniation solution is 10-50%; the amination solution is at least one of aqueous solution of trimethylamine, triethylamine, tripropylamine, tributylamine, N-methylimidazole or pyridine;
(5) and (4) soaking the precursor of the aminated composite alkaline polymer electrolyte membrane in a concentration alkaline solution for alkali exchange, taking out after soaking for 24-48h at room temperature, and washing with deionized water until the pH value of a washing liquid is 7 to obtain the composite alkaline polymer electrolyte membrane.
Based on the above technical solution, preferably, the block-type polymer solution in step (1) of the present invention mainly comprises at least one of diblock copolymers and triblock copolymers: diblock copolymers including styrene-butylene block copolymers (SBS), acrylonitrile-styrene copolymers, styrene-oxyethylene copolymers, styrene-acrylic copolymers, styrene-ethylene copolymers; styrene-ethylene-butylene block copolymers (SEBS), styrene-oxyethylene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-ethylene-styrene copolymers (AES), acrylonitrile-styrene-acrylate copolymers (ASA), styrene-isoprene-styrene copolymers, the styrene block content of the block polymers being 10-60 wt.%. Based on the above technical scheme, preferably, the solvent a in step (1), the solvent C in step (2) and the solvent D in step (3) are independently selected from at least one of chloroform, tetrahydrofuran, dichloroethane, trichloroethane and tetrachloroethane; the solvent B is at least one of ethanol, n-propanol and isopropanol.
Based on the technical scheme, preferably, the catalyst in the step (1) is one or more of anhydrous zinc chloride, anhydrous aluminum chloride or anhydrous tin chloride, and the mass ratio of the block polymer to the catalyst is 1: 2-10; the chloromethylation reagent is 1, 4-dichloromethoxybutane (BCMB).
Based on the technical scheme, preferably, in the high-pressure electrostatic spinning technology in the step (3), the distance between a needle and a collector is 3-20cm, the feeding speed of the resin slurry of the fiber porous membrane layer is 0.1-3.0mL/h, the spinning voltage is 1-30kV, the ambient temperature is 10-50 ℃, and the relative humidity is less than 30%.
Based on the technical scheme, preferably, in the step (3), the hot pressing pressure is 0.1-5MPa, the hot pressing temperature is 10-80 ℃, and the hot pressing time is 1-30 min; the surface coating is to spray or brush the solvent D on the surface of the compact film layer or the fiber porous film layer and then attach the compact film layer and the fiber porous film layer; and the step of pouring and immersing is to pour and immerse the spinning porous layer by using a solvent D and then attach the spinning porous layer to the compact film layer.
Based on the technical scheme, preferably, the alkaline solution in the step (4) is a sodium hydroxide solution and/or a potassium hydroxide solution, and the concentration of the alkaline solution is 0.01-10 mol/L.
In still another aspect, the present invention provides an application of the composite alkaline polymer electrolyte membrane in an alkaline fuel cell, wherein the composite alkaline polymer electrolyte membrane prepared by the method has good ion and water transfer characteristics, exhibits high ionic conductivity (25 mS/cm at 60 ℃ and 32mS/cm at 80 ℃), and exhibits good performance (779 mW/cm at 60 ℃) when applied to an alkaline fuel cell2)。
Advantageous effects
The prepared composite alkaline polymer electrolyte membrane has good ion and water transfer characteristics, shows high ion conductivity (25 mS/cm at 60 ℃ and 32mS/cm at 80 ℃), and shows good performance when applied to an alkaline fuel cell (779 mW/cm at 60 ℃)2). The alkaline polymer electrolyte membrane can be effectively produced in a laminating mode and is suitable for different environments, the preparation method is simple, the multi-needle spinning linkage can be utilized, the large-scale manufacturing is realized, and the industrial value is very high.
Drawings
FIG. 1 is a sectional electron microscope image of a composite alkaline polymer electrolyte membrane prepared in example 1.
FIG. 2 is an electron microscope image of a composite alkaline polymer electrolyte membrane fiber porous membrane layer prepared in example 1.
FIG. 3 is an electron microscope image of the dense film layer of the composite alkaline polymer electrolyte membrane prepared in example 1.
Fig. 4 is a graph showing the change in Cl ionic conductivity with time of the composite type alkaline polymer electrolyte membrane prepared in example 2.
FIG. 5 shows examples 2 and 5H of the films prepared in example 6 and comparative example 12/O2Fuel cell performance maps.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Example 1
(1) (production of anion-conducting resin precursor a)
Dissolving 1g of styrene-ethylene-butylene block copolymer (SEBS) in 30g of organic reagent chloroform, adding 2.17g of anhydrous tin chloride as a catalyst, adding 4.18g of 1, 4-dichloromethoxybutane (BCMB) as a chloromethylation reagent, stirring and reacting at 55 ℃ for 6 hours, pouring the reaction solution into 100g of ethanol, separating out white flocculent precipitate, filtering, and drying to obtain the anion-conductive resin precursor a.
(2) Dissolving 0.1g of the anion-conducting resin precursor a in 1.9g of tetrahydrofuran, stirring at room temperature for 6h to obtain dense film layer resin slurry, and uniformly pouring into a container with the thickness of 100cm2And (3) putting the flat-plate mold into a drying oven at 60 ℃, keeping the temperature for 24 hours, and evaporating the solvent to obtain a compact film layer of the composite alkaline polymer electrolyte film. And taking off the compact film layer of the composite alkaline polymer electrolyte film, and adopting an aluminum foil as a substrate to cling to a collector of a roller type high-voltage electrostatic spinning machine.
(3) And dissolving 0.1g of the anion-conducting resin precursor a in 1.9g of tetrachloroethane to form a 5 wt.% solution, stirring at room temperature for 6 hours to obtain fiber porous membrane layer resin slurry, filling the fiber porous membrane layer resin slurry into an injection device with a needle head, and fixing the fiber porous membrane layer resin slurry on a support of a high-voltage electrostatic spinning machine. The distance between a high-voltage electrostatic spinning needle and the collector is 10cm, the feeding speed of the resin slurry of the fiber porous membrane layer is 0.5mL/h, and the spinning area is 200cm2And the voltage is adjusted to 10kV, the ambient temperature is 25 ℃, the relative humidity is 10 percent, and the fiber porous membrane layer resin slurry is spun on the composite alkaline polymer electrolyte membrane compact membrane layer tightly attached to the collector of the roller type high-voltage electrostatic spinning machine to obtain the precursor of the composite alkaline polymer electrolyte membrane.
(4) (functionalization and base exchange of composite alkaline Polymer electrolyte Membrane precursors)
And soaking the composite alkaline polymer electrolyte membrane precursor in 33 wt.% of trimethylamine aqueous solution for further functionalization (ammonification), taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the ammonified composite alkaline polymer electrolyte membrane precursor. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and obtaining the composite alkaline polymer electrolyte membrane.
Example 2
A composite basic polymer electrolyte membrane was obtained by changing the mass of the anion-conductive resin precursor in step (2) and step (3) of example 1 to 0.4g and 0.2g, respectively, and adding the reagents in the same proportions as in example 1.
Example 3
A composite basic polymer electrolyte membrane was obtained by changing the mass of the anion-conductive resin precursor in step (2) and step (3) of example 1 to 0.6g and 0.3g, respectively, and adding the reagents in the same proportions as in example 1.
The composite type alkaline polymer electrolyte membranes obtained in examples 1 to 3 were tested for the thickness of the dense membrane layer and the fibrous porous membrane layer, and the results are shown in table 1.
TABLE 1
Figure BDA0002040613590000061
Fig. 1 is a sectional electron microscope image of the composite alkaline polymer electrolyte membrane prepared in example 1, wherein the left side of the section is a 10um fiber porous membrane layer, and the right side is a 5um dense membrane layer, so that the obvious morphology difference of two sides can be seen from the image, but no obvious boundary exists due to the consistent materials. FIG. 2 is an electron microscope image of the dense film layer of the composite alkaline polymer electrolyte membrane prepared in example 1, from which it can be seen that the surface is smooth, dense and pinhole-free. FIG. 3 is an electron microscope image of the porous membrane layer of the composite alkaline polymer electrolyte membrane fiber prepared in example 1, from which it can be seen that the morphology is fibrous, the diameter of the fiber is less than 5um, the distribution is uniform, the porosity is high, and through holes can be formed.
To characterize the anion conductivity, the conductivity was tested, FIG. 4 shows the Cl ion conductivity of example 2 as a function of temperature, showing that the membrane conductivity increases with increasing temperature, reaching above 32mS/cm at 80 deg.C, and FIG. 5 shows the H ion conductivity of example 22/O2Fuel cell performance, fuel cell performance test conditions: the anode and the cathode respectively adopt PtNi/C and Pt/C electrodes; a hydrogen/oxygen stoichiometric ratio of 2/3; the temperature of the hydrogen/oxygen humidifying tank is 60/50 ℃; the temperature of the hydrogen/oxygen heating belt is 60 ℃; the temperature of the battery is 60 ℃; the hydrogen/oxygen back pressure of the battery is 0.1 MPa. The highest power density is 779mW/cm2. Can have great application prospect in alkaline fuel cells.
Example 4
(1) (production of anion-conducting resin precursor b)
Dissolving 1g of styrene-ethylene copolymer in 30g of organic reagent chloroform, adding 3.2g of anhydrous zinc chloride as a catalyst, adding 4.18g of 1, 4-dichloromethoxybutane (BCMB) as a chloromethylation reagent, stirring and reacting at 50 ℃ for 6 hours, pouring the reaction solution into 100g of ethanol, separating out white flocculent precipitate, filtering and drying to obtain the anion-conductive resin precursor b.
(2) Dissolving 0.4g of the anion-conducting resin precursor b in 7.6g of tetrahydrofuran to form a 5 wt.% solution, stirring at room temperature for 6h to obtain dense membrane layer resin slurry, and uniformly pouring into a container with the thickness of 100cm2And (3) putting the flat-plate mold into a drying oven at 60 ℃, keeping the temperature for 24 hours, and evaporating the solvent to obtain a compact film layer of the composite alkaline polymer electrolyte film.
(3) 0.2g of the anion-conducting resin precursor a prepared in example 1 was dissolved in 3.8g of tetrachloroethane to form a 5 wt.% solution, which was stirred at room temperature for 6 hours to obtain a fiber porous membrane layer resin slurry, which was poured into an injection device with a needle and fixed on a holder of a high-pressure electrospinning machine, the distance from the high-pressure electrospinning needle to the collector was 10cm, the feeding rate of the fiber porous membrane layer resin slurry was 0.5mL/h, and the spinning area was 200cm2The voltage is adjusted to 10kV, the ambient temperature is 25 ℃, and the temperature is relatively wetAnd the degree is 10 percent, spinning the spinning resin slurry on a flat plate type collector to obtain a fiber porous membrane layer of the precursor of the composite alkaline polymer electrolyte membrane.
(4) And respectively removing the compact film layer and the fiber porous film layer of the composite alkaline polymer electrolyte membrane, and stacking the compact film layer and the fiber porous film layer. And hot pressing for 3min at 60 ℃ under 2MPa by using a flat plate type oil press to obtain the precursor of the composite alkaline polymer electrolyte membrane.
(5) And soaking the composite alkaline polymer electrolyte membrane precursor in 33 wt.% of trimethylamine aqueous solution for further ammonification, taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the ammonified composite alkaline polymer electrolyte membrane precursor. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and obtaining the composite alkaline polymer electrolyte membrane.
Example 5
(1) The dense membrane layer and the fibrous porous membrane layer of the composite alkaline polymer electrolyte membrane were obtained as described in the steps (1) to (3) in example 4.
(2) And uniformly spraying a small amount of tetrachloroethane on the compact film layer, flatly paving and attaching the fiber porous film layer on the compact film layer, and drying to obtain the precursor of the composite alkaline polymer electrolyte membrane.
(3) And soaking the composite alkaline polymer electrolyte membrane precursor in 33 wt.% of trimethylamine aqueous solution for further ammonification, taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the ammonified composite alkaline polymer electrolyte membrane precursor. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and obtaining the composite alkaline polymer electrolyte membrane.
Example 6
(1) The dense membrane layer and the fibrous porous membrane layer of the composite alkaline polymer electrolyte membrane were obtained as described in the steps (1) to (3) in example 4.
(2) And uniformly spraying a small amount of tetrachloroethane on two sides of the compact membrane layer, respectively tiling and jointing two fiber porous membrane layers on two sides of the compact membrane layer, and drying to obtain a three-layer composite alkaline polymer electrolyte membrane precursor.
(3) And soaking the composite alkaline polymer electrolyte membrane precursor in 33 wt.% of trimethylamine aqueous solution for further ammonification, taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the ammonified composite alkaline polymer electrolyte membrane precursor. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and obtaining the composite alkaline polymer electrolyte membrane.
Comparative example 1
0.8g of the anion-conducting resin precursor a obtained in example 1 was dissolved in 15.2g of tetrahydrofuran to form a 5 wt.% solution, which was stirred at room temperature for 6 hours to obtain a dense film resin slurry, which was poured uniformly into a 100cm container2And (3) putting the flat-plate mold into a drying oven at 60 ℃, keeping the temperature for 24 hours, and evaporating the solvent to obtain the compact alkaline polymer electrolyte membrane precursor with the thickness of 40 um.
And soaking the precursor of the compact alkaline polymer electrolyte membrane in a trimethylamine aqueous solution of 33 wt.% for further ammonification, taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the precursor of the compact alkaline polymer electrolyte membrane subjected to ammonification. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and obtaining the compact alkaline polymer electrolyte membrane.
Use of H from comparative example 12/O2Fuel cell performance as shown in fig. 5, fuel cell performance test conditions: the anode and the cathode respectively adopt PtNi/C and Pt/C electrodes; a hydrogen/oxygen stoichiometric ratio of 2/3; the temperature of the hydrogen/oxygen humidifying tank is 60/50 ℃; the temperature of the hydrogen/oxygen heating belt is 60 ℃; the temperature of the battery is 60 ℃; the hydrogen/oxygen back pressure of the battery is 0.1 MPa. The highest power density is 420mW/cm2. Comparative examples 2 and 6 of the present invention composite type alkaline polymer electrolyte membranes H2/O2The performance of the fuel cell can be known, and the inventionThe composite alkaline polymer electrolyte membrane has more excellent performance.
Comparative example 2
0.2g of the anion-conducting resin precursor a prepared in example 1 was dissolved in 3.8g of tetrachloroethane to form a 5 wt.% solution, which was stirred at room temperature for 6 hours to obtain a resin slurry for a fiber porous membrane layer, which was poured into an injection device with a needle and fixed on a holder of a high-voltage electrostatic spinning machine. The distance between a high-voltage electrostatic spinning needle and the collector is 10cm, the feeding speed of the resin slurry of the fiber porous membrane layer is 0.5mL/h, and the spinning area is 200cm2And the voltage is adjusted to 10kV, the ambient temperature is 25 ℃, the relative humidity is 10%, and the spinning resin slurry is spun on a flat plate collector to obtain the fiber porous alkaline polymer electrolyte membrane precursor with the thickness of 40 um.
Soaking the fiber porous alkaline polymer electrolyte membrane precursor in a trimethylamine aqueous solution of 33 wt.% for further ammonification, taking out after soaking at room temperature for 24h, and washing with deionized water for more than 2 times to obtain the ammonified fiber porous alkaline polymer electrolyte membrane precursor. And then soaking in a potassium hydroxide aqueous solution with the concentration of 1mol/L for 24 hours at room temperature, taking out, washing with deionized water until the pH value of a washing liquid is 7, and thus obtaining the fiber porous alkaline polymer electrolyte membrane.
When the cell was assembled using comparative example 2, it was found that when nitrogen was introduced at the positive and negative stages, a constant pressure could not be maintained after applying a back pressure to either side, since the gas could directly penetrate the fibrous porous membrane layer. Therefore, the cathode and anode gases cannot be blocked only by using the fiber porous membrane layer, and the application is not suitable.

Claims (8)

1. A preparation method of a composite alkaline polymer electrolyte membrane is characterized by comprising the following steps: the preparation method comprises the following steps: (1) forming a composite membrane layer by arranging n layers of dense membrane layers and m layers of fiber porous membrane layers in a mutually crossed manner, (2) carrying out ammonification and alkali exchange on the composite membrane layer to obtain the composite alkaline polymer electrolyte membrane; the compact film layer is prepared by a casting method of a block polymer subjected to chloromethylation; the fiber porous membrane layer is prepared by a block polymer subjected to chloromethylation through an electrostatic spinning technology; the block polymer is a diblock or triblock polymer containing a styrene block; n is more than or equal to 1, m is more than or equal to 1, and n and m are integers; the porosity of the compact film layer is less than 0.1%; the porosity of the fiber porous membrane layer is 10-80%;
the preparation method of the electrolyte membrane comprises the following steps:
(1) dissolving the block polymer in a solvent A, adding a catalyst and a chloromethylation reagent, stirring and reacting at 40-80 ℃ for 4-12h, separating out a reactant by using a solvent B, filtering, washing and drying to obtain an anion-conductive resin precursor; the mass ratio of the block polymer to the organic solvent A to the catalyst to the chloromethylation reagent is 1: 20-100: 1-5: 2-10;
(2) dissolving the anion-conducting resin precursor in the step (1) in a solvent C, stirring at 10-60 ℃ for 0.1-24h to obtain compact film resin slurry, pouring the compact film resin slurry into a flat plate type mould, putting the flat plate type mould into a drying box at 25-100 ℃, and keeping the temperature for 6-48h to obtain a compact film; the mass ratio of the anion-conducting resin precursor to the solvent C is 1: 5-100;
(3) dissolving the anion-conductive resin precursor in the step (1) in a solvent D, stirring at 10-60 ℃ for 0.1-24h to obtain fiber porous membrane layer resin slurry, a: spinning the fiber porous membrane layer resin slurry on one side of the compact membrane layer in the step (2) by adopting an electrostatic spinning technology to obtain a precursor of the composite alkaline polymer electrolyte membrane, or b: carrying out electrostatic spinning on the fiber porous membrane layer resin slurry to obtain a fiber porous membrane layer, and carrying out hot pressing, surface coating or pouring immersion on the fiber porous membrane layer and the compact membrane layer obtained in the step (2) to obtain a precursor of the composite alkaline polymer electrolyte membrane; the mass ratio of the anion-conducting resin precursor to the solvent D is 1: 5-100;
(4) dissolving the precursor of the composite alkaline polymer electrolyte membrane obtained in the step (3) in an ammonium solution, soaking for 24-48h at 25-60 ℃, washing and drying to obtain an ammonium composite alkaline polymer electrolyte membrane precursor; the concentration of the ammoniated solution is 10-50 wt.%; the amination solution is at least one of aqueous solution of trimethylamine, triethylamine, tripropylamine, tributylamine, N-methylimidazole or pyridine;
(5) soaking the precursor of the ammonium compound type alkaline polymer electrolyte membrane in an alkaline solution for 24-48h to obtain the compound type alkaline polymer electrolyte membrane;
the solvent A in the step (1), the solvent C in the step (2) and the solvent D in the step (3) are independently selected from at least one of chloroform, tetrahydrofuran, dichloroethane, trichloroethane and tetrachloroethane; the solvent B is at least one of ethanol, n-propanol and isopropanol.
2. The method of claim 1, wherein the dense membrane layer has a thickness of 1-200 um; the thickness of the fiber porous film layer is 1-200um, and the fiber diameter is 0.1-5 um.
3. The production method according to claim 1, wherein the block-type polymer comprises at least one of a diblock copolymer and a triblock copolymer; the diblock copolymer comprises styrene-butadiene copolymer, acrylonitrile-styrene copolymer, styrene-oxyethylene copolymer, styrene-acrylic acid copolymer and styrene-ethylene copolymer; the triblock copolymer comprises a styrene-ethylene-butylene block copolymer, a styrene-oxyethylene-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, an acrylonitrile-ethylene-styrene copolymer and a styrene-isoprene-styrene copolymer, and the content of styrene blocks in the block copolymer is 10-60 wt.%.
4. The preparation method according to claim 1, wherein the catalyst in step (1) is at least one of anhydrous zinc chloride, anhydrous aluminum chloride or anhydrous tin chloride; the chloromethylation reagent is 1, 4-dichloromethoxybutane (BCMB).
5. The preparation method according to claim 1, wherein the hot pressing pressure in the step (3) is 0.1 to 5MPa, the hot pressing temperature is 10 to 80 ℃, and the hot pressing time is 1 to 30 min; the surface coating is to spray or brush the solvent D on the surface of the compact film layer or the fiber porous film layer and then attach the compact film layer and the fiber porous film layer; and the step of pouring and immersing is to use a solvent D to pour and immerse the fiber porous membrane layer and then attach the fiber porous membrane layer to the compact membrane layer.
6. The preparation method according to claim 1, wherein the alkaline solution in the step (4) is a sodium hydroxide solution and/or a potassium hydroxide solution, and the concentration of the alkaline solution is 0.01-10 mol/L.
7. The preparation method according to claim 1, wherein the control parameters of the electrostatic spinning in the step (3) are as follows: the distance between the electrostatic spinning needle and the collector is 3-20cm, the feeding speed of the resin slurry of the fiber porous film layer is 0.1-3.0mL/h, the spinning voltage is 1-30kV, the ambient temperature is 10-50 ℃, and the relative humidity is less than 30%.
8. Use of a composite alkaline polymer electrolyte membrane prepared according to the method of claim 1 in an alkaline membrane fuel cell.
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