CN112194810B - Method for preparing polybenzimidazole-based porous polymer ion exchange membrane by adopting gas-phase induced phase conversion method and application thereof - Google Patents

Method for preparing polybenzimidazole-based porous polymer ion exchange membrane by adopting gas-phase induced phase conversion method and application thereof Download PDF

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CN112194810B
CN112194810B CN202010902538.7A CN202010902538A CN112194810B CN 112194810 B CN112194810 B CN 112194810B CN 202010902538 A CN202010902538 A CN 202010902538A CN 112194810 B CN112194810 B CN 112194810B
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ion exchange
polybenzimidazole
exchange membrane
porous polymer
polymer ion
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CN112194810A (en
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李南文
胡旭
黄瑛达
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase conversion method and application thereof. The porous membrane can realize the transmission of ion exchange without ion exchange groups. The porous membrane with controllable pore structure, low cost and easy industrialization can be prepared by using a gas-phase induced phase conversion method. The porous membrane prepared by the invention is applied to the alkaline water electrolysis cell after being doped with alkali, shows high ionic conductivity and stable mechanical property, and has very good application prospect on the alkaline water electrolysis cell.

Description

Method for preparing polybenzimidazole-based porous polymer ion exchange membrane by adopting gas-phase induced phase conversion method and application thereof
Technical Field
The invention belongs to the technical field of alkaline water electrolyzers, and particularly relates to a method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase conversion method and application thereof.
Background
Electrochemical energy storage technology (i.e. the electrochemical decomposition of water to store the surplus electrical energy of renewable energy in the form of hydrogen) is currently receiving increasing attention (IEEE,2012,100,410). Proton Exchange Membrane (PEM) systems based on perfluorosulfonic acid membranes can produce high-purity hydrogen when operated at high current densities, but are limited by electrode materials and catalysts in acidic environments, so that large-scale application of the PEM systems is prevented, people begin to turn into the traditional alkaline water electrolyzer technology, and oxidation-reduction reactions which are relatively easy to occur under alkaline conditions promote selection of abundant and cheap materials and catalysts, which is an important aspect of large-scale implementation. Conventional alkaline water electrolysers are durable and robust systems that have been marketed for a long time, but the conventional systems have high internal resistance. Therefore, shortening the inter-electrode distance should be a key strategy to develop cost-effective, superior performance advanced alkaline water electrolysers (j. electrochem. soc.,2016,163, F3197).
A hot approach to achieve this goal is to replace the porous membrane with an anion exchange membrane. This makes possible cell designs with electrode spacings of less than 100mm, i.e. direct contact of gas diffusion electrodes with the membrane (j. hydrogen energy, 2011,36,15089), and therefore anion exchange membranes based on quaternary ammonium salt functionalized polymers have recently received much attention, but improving the polymer backbone structure to improve long term stability and the anion exchange moiety in the hydroxide ionomer form remains a formidable challenge.
Another alternative is to build an electrolytic cell around the ion-solvating electrolyte membrane system formed by the porous polymer with heterocyclic rings doped with alkali solution, the conjugated structure in the polymer with heterocyclic rings has basicity, so that these types of polymers can transport protons or OH after doping with acid or alkali-The mechanical stability and air tightness of the polymer and the conductivity of the alkaline aqueous salt solution are combined to form a ternary system. The system was first investigated by Xing and Savadogo, showing that its ionic conductivity is within the practical range (electrochem. commun.,2000,2, 697). Research has been conducted on technical applications as hydrogen electrolytes in electrode binders, alcohols, fuel cells and supercapacitors.
Porous membranes are prepared by a number of methods including phase inversion, coating, template impregnation, track etching, and the like. Among them, the phase inversion method is most commonly used, such as vapor phase precipitation, thermal precipitation, immersion precipitation, etc. The gas-phase induced phase transformation can enable the phase transformation process to be carried out under the condition close to a steady state, and the prepared porous membrane has uniform aperture and thinner skin layer. The membrane is doped with alkali liquor, so that the conductivity and the liquid holding capacity of hydroxide ions of the membrane can be increased, and the membrane has a good prospect when being applied to an alkaline water electrolyzer.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by using a gas-phase induced phase conversion method, which has higher electrolyte absorption rate, excellent thermal stability and good mechanical properties, and an application thereof.
The design concept of the invention is as follows: the preparation method is characterized in that one or more of benzimidazole organic high molecular polymers are used as raw materials, and a gas phase induction phase conversion method is adopted to prepare the benzimidazole organic high molecular polymers, wherein the gas phase is a poor solvent steam atmosphere of the benzimidazole organic high molecular polymers.
The invention is realized by the following technical scheme.
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
(1) dissolving one or more organic high molecular polymers with benzimidazole structures serving as raw materials in a mixed solvent, fully stirring at the temperature of 5-300 ℃ for 0.5-24 h to prepare a casting solution with the raw materials completely dissolved, standing and defoaming the casting solution, wherein the concentration of the organic high molecular polymers with heterocycles in the casting solution is 1-70 wt%; the mixed solvent comprises an organic solvent and a volatile solvent, the concentration of the volatile solvent in the mixed solvent is 0-50 wt%, and the volatile solvent is heated to volatilize so that the reaction system is in the poor solvent steam atmosphere of the organic high molecular polymer;
(2) pouring the casting solution prepared in the step (1) onto a non-woven fabric substrate or directly onto a clean and flat glass plate, and scraping the casting solution into a liquid film by using a scraper;
(3) under normal pressure, the liquid film prepared in the step (2) is in the poor solvent steam atmosphere of the organic high molecular polymer, the poor solvent steam atmosphere accounts for 1-100% of the total volume of air, the temperature is controlled at 50-200 ℃, the time is controlled at 0.1-2 hours, the phase conversion process of the liquid film from a liquid phase to a gas phase is completed, and the polymer film is prepared;
(4) firstly, the polymer film prepared in the step (3) is placed in deionized water to be soaked for 0.1 to 24 hours at the temperature of 0 to 100 ℃; then, washing away the residual solvent to obtain the polybenzimidazole-based porous polymer ion exchange membrane, wherein the chemical structure formula is as follows:
Figure BDA0002660258330000021
the polymer of the porous polymer ion exchange membrane is a homopolymer or a random copolymer, wherein n represents the degree of polymerization, n is a positive integer of 10-200, and the weight average molecular weight is 5000-; in the formula, R has a structure that multiple irregular bulky groups are positioned in a main chain, and the distance between polymer chains is increased, so that alkali liquor is easily doped to form salts, the transmission of ions is improved, the function of intermolecular hydrogen bonds is reduced, and the improvement of the solubility is facilitated. -R-represents one or more of the following structures:
Figure BDA0002660258330000031
when the porous polymer film is prepared by the gas-phase induced phase conversion method, the sizes and the distribution of the pores on the upper surface, the lower surface and the cross section of the porous film are adjusted by controlling factors such as a solvent, film forming time, temperature, humidity and the like, so that the liquid holding capacity and other performances of the porous film are further optimized, and the potential of the porous film in the application of an alkaline water electrolyzer is expanded.
Further, the porous polymer ion exchange membrane prepared in the step (4) has the aperture size of 0.05-100 nm, the porosity of 1-200% and the thickness of 10-500 μm.
Further, in the step (1), the organic solvent is one or more of DMSO, DMAc, NMP, DMF or MSA; the volatile solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran or n-hexane.
Further, in the step (1), the vapor atmosphere of the poor solvent of the organic high molecular polymer is one or more of water vapor, methanol vapor, ethanol vapor, propanol vapor, butanol vapor, pentanol vapor, methyl ether vapor, ethyl ether vapor, formic acid vapor, and acetic acid vapor.
The application of a method for preparing a porous polymer ion exchange membrane based on polybenzimidazole by adopting a gas-phase induced phase inversion method comprises the following steps:
(1) soaking the polybenzimidazole-based porous polymer ion exchange membrane prepared in the step (4) in an alkaline solution at the temperature of 80 ℃ for 10-72 hours, wherein the concentration of the alkaline solution is 1-50 wt%;
(2) and (2) installing the alkali-doped porous polymer ion exchange membrane prepared in the step (1) in an alkaline water electrolyzer device.
(2.1) preparation of MEA of the Water Electrolysis apparatus, and preparation of anode and cathode by Catalyst Coated Substrate (CCS) method. The anode was prepared as follows: IrO is to be mixed2The powder was mixed with deionized water and isopropanol and then the PTFE emulsion was added. After 30 minutes of sonication, the catalyst ink was stirred in a water bath at 85 ℃ and water and isopropanol were evaporated. The paste obtained was coated on a platinized porous Ti plate. An ionomer solution (a commercial ionomer at 5 wt% solids in ethanol) was also sprayed onto the surface of the catalyst layer, drying the ionomer and IrO2The loading amounts in the anode were 1.5 and 8 mg-cm, respectively-2. For the cathode preparation, Pt/C (40 wt%), deionized water, isopropanol, and PTFE emulsion (6 wt% in the cathode) were mixed, and the prepared ink was sonicated for 30 minutes and sprayed on carbon paper with a Pt loading of 0.4mg cm-2. The ionomer solution was also sprayed on the surface (1.5mg cm)-2). The electrode area is 5cm2. Finally, both electrodes were immersed in 1M NaOH for 24h for ion exchange and rinsed several times with deionized water before use.
(2.2) sandwiching the membrane electrode between the cathode and the anode to assemble the electrolytic water device. A platinized porous Ti plate was used as a current collector in the cathode. Electrochemical tests were carried out in immersion in the anolyte and catholyte solutions, the polarization curves obtained by measuring the cell voltage at different current densities with varying temperature, and at 50 ℃,200 mA · cm-2The durability thereof was evaluated at a constant current.
Further, the alkaline solution doped by the porous polymer ion exchange membrane is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate; the electrolyte in the electrolytic cell device is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate and pure water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the porous polymer ion exchange membrane prepared by the invention is applied to alkaline water electrolysis, the sizes and the distribution of the upper surface, the lower surface and the cross section holes of the porous membrane are adjusted by controlling factors such as solvent, membrane forming time, temperature, humidity and the like, the ion permeation selectivity of the membrane is kept, the porous polymer ion exchange membrane can be applied to an alkaline water electrolysis cell, and the reduction of the oxidation stability of the polymer caused by the introduction of ion exchange groups in the conventional membrane is avoided.
(2) The porous polymer ion exchange membrane prepared by the invention is subjected to phase transformation in a gas phase, the phase transformation process is carried out under the condition close to a steady state, the prepared porous membrane has uniform aperture and thinner skin layer, and the prospect of applying the membrane doped with alkali liquor to an alkaline water electrolyzer is very good.
(3) The prepared porous polymer ion exchange membrane electrolytic cell has the stability of more than 500h (50 ℃,200 mA/cm)2)。
(4) The prepared porous polymer electrolyte membrane has good thermal stability and mechanical property, the decomposition temperature of the polymer is higher than 600 ℃, and the glass transition temperature is higher than 400 ℃.
(5) The membrane has simple preparation method, easy regulation and control of pore diameter, low cost and easy realization of mass production.
(6) The invention widens the variety and application range of membrane materials for the alkaline water electrolyzer technology.
Drawings
FIG. 1 is a TGA curve of the thermal stability of the porous polymer electrolyte membrane prepared in example 1.
FIG. 2 is a stability test curve of the porous polymer ion-exchange membrane prepared in example 1 on an alkaline water electrolyzer.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example one
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by using a gas-phase induced phase inversion method as shown in fig. 1 and 2, comprising the steps of:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt.% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 60% for 20 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. alkaline water electrolyzer assembled by using prepared porous membrane
(1) Immersing the porous polymer film prepared in the step into 1-50 wt% of alkali solution at 80 ℃ for 10-72 h;
(2) applying an alkali-doped porous polymer membrane to an alkaline water electrolyzer unit;
(2.1) preparation of MEA of the Water Electrolysis apparatus, and preparation of anode and cathode by Catalyst Coated Substrate (CCS) method. The anode was prepared as follows: IrO is to be mixed2The powder was mixed with deionized water and isopropanol and then the PTFE emulsion was added. After 30 minutes of sonication, the catalyst ink was stirred in a water bath at 85 ℃ and water and isopropanol were evaporated. The paste obtained was coated on a platinized porous Ti plate. An ionomer solution (commercial ionomer at 5 wt% solids in ethanol) was also sprayed onto the surface of the catalyst layer, drying the ionomer and IrO2The loading amounts in the anode were 1.5 and 8 mg-cm, respectively-2. For the cathode preparation, Pt/C (40 wt%), deionized water, isopropanol, and PTFE emulsion (6 wt% in the cathode) were mixed, and the prepared ink was sonicated for 30 minutes and sprayed on carbon paper with a Pt loading of 0.4mg cm-2. The ionomer solution was also sprayed on the surface (1.5mg cm)-2). The electrode area is 5cm2. Finally, both electrodes were immersed in 1m naoh for 24h for ion exchange and rinsed several times with deionized water before use;
(2.2) sandwiching the membrane electrode between the cathode and the anode to assemble the electrolytic water device. A platinized porous Ti plate was used as a current collector in the cathode. Electrochemical tests were carried out in immersion in the anolyte and catholyte solutions, the polarization curves obtained by measuring the cell voltage at different current densities with varying temperature, and at 50 ℃,200 mA · cm-2The durability thereof was evaluated at a constant current.
Example two
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt.% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 70% for 20 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE III
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt.% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 80% for 20 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example four
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt.% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 90% for 20 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE five
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 100% for 20 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE six
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 60% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE seven
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 70% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example eight
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 80% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example nine
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 90% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example ten
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -. 10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 100% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE eleven
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) is dissolved in DMF at room temperature and stirred for 1 hour to prepare 12.5 weight percent of uniform and transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 60% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example twelve
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) is dissolved in DMF at room temperature and stirred for 1 hour to prepare 12.5 weight percent of uniform and transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 70% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
EXAMPLE thirteen
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) is dissolved in DMF at room temperature and stirred for 1 hour to prepare 12.5 weight percent of uniform and transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 80% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example fourteen
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) is dissolved in DMF at room temperature and stirred for 1 hour to prepare 12.5 weight percent of uniform and transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -.10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 90% for 10 min. Then taking out the glass plate and immersing the glass plate into 3 liters of deionized water at room temperature for 30min, and washing the porous membrane cleanly and taking out the porous membrane;
3. the specific steps of using the prepared porous membrane to assemble the alkaline water electrolyzer are the same as the first embodiment.
Example fifteen
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a gas-phase induced phase inversion method comprises the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) is dissolved in DMF at room temperature and stirred for 1 hour to prepare 12.5 weight percent of uniform and transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by gas phase induced phase inversion method
The method comprises the following steps: the mPBI homogeneous solution with a concentration of 12.5 wt% was knife-coated onto a glass plate to spread a solution film with an average thickness of 40. + -. 10 μm, and then the glass plate with the attached liquid film was rapidly placed in an air atmosphere at 80 ℃ and a humidity of 100% for 10 min. The glass plate was then removed and immersed in 3 liters of deionized water at room temperature for 30min, and the porous membrane was washed clean and removed.
Comparative example
This example of a process for the preparation of a compact polybenzimidazole-based polymer comprising the following steps:
1. preparation of homogeneous film-forming solution
The method comprises the following steps: polybenzimidazole (mPBI) was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting film solution;
2. preparation of porous polybenzimidazole polymer electrolyte membrane by tape casting method
The method comprises the following steps: the PBI homogeneous solution with the concentration of 12.5 wt% is blade-coated on a glass plate to be spread into a solution film with the average thickness of 40 +/-10 mu m, the solution film is placed in an oven with the temperature of 80 ℃ for 12 hours, then the glass plate is taken out and immersed in 3 liters of deionized water at the room temperature for 30 minutes, and the porous film is washed clean and taken out. Then drying for 24 hours at room temperature, and then drying for 12 hours at 80 ℃ under a vacuum condition;
3. the specific steps of the alkaline water electrolyzer assembled by the prepared membrane are the same as the first embodiment.
In summary, the performance comparison table of the polymer ion exchange membranes prepared in all the examples and comparative examples is shown below.
Figure BDA0002660258330000111
Figure BDA0002660258330000121
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (4)

1. The application of preparing the porous polymer ion exchange membrane based on the polybenzimidazole by adopting a gas-phase induced phase inversion method is characterized by comprising the following steps of:
(1) soaking a polybenzimidazole-based porous polymer ion exchange membrane in an alkaline solution at the temperature of 80 ℃ for 10-72 hours, wherein the concentration of the alkaline solution is 1-50 wt%; the alkaline solution doped in the porous polymer ion exchange membrane is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate;
(2) installing the alkali-doped porous polymer ion exchange membrane prepared in the step (1) in an alkaline water electrolyzer device; the electrolyte in the electrolytic cell device is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate and pure water;
the preparation method of the polybenzimidazole-based porous polymer ion exchange membrane comprises the following steps:
a. dissolving one or more of organic high molecular polymers with benzimidazole structures serving as raw materials in a mixed solvent, fully stirring at the temperature of 5-300 ℃ for 0.5-24 h to prepare a casting solution with the raw materials completely dissolved, standing the casting solution for defoaming, wherein the concentration of the organic high molecular polymers with the benzimidazole structures in the casting solution is 1-70 wt%; the mixed solvent comprises an organic solvent and a volatile solvent, the concentration of the volatile solvent in the mixed solvent is 0-50 wt%, and the volatile solvent is heated to volatilize so that the reaction system is in the poor solvent steam atmosphere of the organic high molecular polymer;
b. pouring the casting solution prepared in the step a onto a non-woven fabric substrate or directly onto a clean and flat glass plate, and scraping the casting solution into a liquid film by using a scraper;
c. b, under normal pressure, placing the liquid film prepared in the step b in a poor solvent steam atmosphere of the organic high molecular polymer, wherein the poor solvent steam atmosphere accounts for 1-100% of the total volume of air, the temperature is controlled at 50-200 ℃, and the time is controlled at 0.1-2 hours, so that the phase conversion process of the liquid film from a liquid phase to a gas phase is completed, and the polymer film is prepared;
d. firstly, the polymer film prepared in the step c is placed in deionized water to be soaked for 0.1 to 24 hours at the temperature of 0 to 100 ℃; then, washing away the residual solvent to obtain the polybenzimidazole-based porous polymer ion exchange membrane, wherein the chemical structure formula is as follows:
Figure FDA0003459154990000011
the polymer of the porous polymer ion exchange membrane is a homopolymer or a random copolymer, wherein n represents the degree of polymerization, n is a positive integer of 10-200, and the weight average molecular weight is 5000-; wherein R is in the structure of a bulky group in the main chain, and-R-represents one or more of the following structures:
Figure FDA0003459154990000021
2. the use of the gas-phase induced phase inversion method according to claim 1 for preparing a polybenzimidazole-based porous polymer ion exchange membrane, wherein: the pore size of the porous polymer ion exchange membrane prepared in the step d is 0.05-100 nm, the porosity is 1-200%, and the thickness is 10-500 microns.
3. The use of the gas-phase induced phase inversion method according to claim 1 for preparing a polybenzimidazole-based porous polymer ion exchange membrane, wherein: in the step a, the organic solvent is one or more of DMSO, DMAc, NMP, DMF or MSA; the volatile solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran or n-hexane.
4. The use of the gas-phase induced phase inversion method according to claim 1 for preparing a polybenzimidazole-based porous polymer ion exchange membrane, wherein: in the step a, the vapor atmosphere of the poor solvent of the organic high molecular polymer is one or more of water vapor, methanol vapor, ethanol vapor, propanol vapor, butanol vapor, pentanol vapor, methyl ether vapor, ethyl ether vapor, formic acid vapor or acetic acid vapor.
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