CN112251774B - Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method - Google Patents

Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method Download PDF

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CN112251774B
CN112251774B CN202010903777.4A CN202010903777A CN112251774B CN 112251774 B CN112251774 B CN 112251774B CN 202010903777 A CN202010903777 A CN 202010903777A CN 112251774 B CN112251774 B CN 112251774B
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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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Abstract

The invention discloses a polybenzimidazole-based porous polymer ion exchange membrane, and a method and application thereof for preparing the same by adopting a sol-gel method. After the film is solidified into a film by a dipping and pulling method, phosphoric acid is still remained in the gel structure of the film, and a spongy compact porous structure is formed after the phosphoric acid is washed away. The prepared porous membrane can realize the transmission of ion exchange without ion exchange groups after being doped by alkali. The sol-gel method has the characteristics of low cost, simple process, easy large-area film formation, easy control of stoichiometric ratio, high product purity and good uniformity. 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

Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method
Technical Field
The invention belongs to the technical field of alkaline water electrolyzers, and relates to a porous polymer ion exchange membrane material, in particular to a polybenzimidazole-based porous polymer ion exchange membrane, and a method for preparing the same by adopting a sol-gel 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 proposal is to build an electrolytic cell around the ion solvation electrolyte membrane system formed by the porous polymer mixed with alkali liquor, and the conjugated structure in the polymer with heterocyclic ring has alkalinity, so that the polymers of the types can transport protons or OH after being mixed 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 variety of methods including sol-gel methods, phase inversion methods, coating methods, track etching methods, and the like. The sol-gel method has the characteristics of low cost, simple process, easy large-area film formation, easy control of stoichiometric ratio, high product purity and good uniformity, and is easier to apply and lower in temperature compared with a gas phase conversion method and a coating method. The properties (porosity, pore size distribution and the like) of the obtained gel strictly depend on the temperature, the solvent, the pH value and the type of the catalyst, so that the sizes and the distribution of the upper surface, the lower surface and the cross-section holes of the porous film need to be further adjusted through the factors, the liquid holding capacity of the porous film is optimized, the conductivity and the stability of hydroxide ions of the film are increased, and the application prospect in an alkaline water electrolyzer is very good.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polybenzimidazole-based porous polymer ion exchange membrane with higher alkali liquor absorption rate, excellent stability and good mechanical property, and a method for preparing the same by adopting a sol-gel method and application thereof.
The design concept of the invention is as follows: the porous membrane is prepared by a sol-gel method, a solution of polybenzimidazole in polyphosphoric acid is cast to form a membrane, and the conversion from a solution state to a gel state is observed in the process of hydrolyzing the solution from polyphosphoric acid (PPA) to Phosphoric Acid (PA). After the film is solidified into a film by a dipping and pulling method, phosphoric acid is still remained in the gel structure of the film, and a spongy compact porous structure is formed after the phosphoric acid is washed away. The prepared porous membrane can realize the transmission of ion exchange without ion exchange groups after being doped by alkali.
The invention is realized by the following technical scheme.
A porous polymer ion exchange membrane based on polybenzimidazole has the following chemical structural general formula:
Figure BDA0002660680570000021
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 BDA0002660680570000031
a method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a sol-gel method comprises the following steps:
(1) firstly, dissolving diacid with a-R-structure and biphenyltetramine in polyphosphoric acid, wherein the concentration of an organic high molecular polymer in a mixed solution is 1-70 wt%; then, adjusting the pH value of the mixed solution to 1-7 to obtain a stable and transparent mixed solution; finally, fully stirring the mixed solution at the temperature of 5-300 ℃ for 0.5-24 h, and carrying out polymerization reaction;
(2) adjusting the temperature of the solution after the polymerization reaction in the step (1) to 190-300 ℃, then slowly immersing the cleaned substrate into the solution after the polymerization reaction, standing for 0.5-30 min, vertically lifting the substrate upwards at the speed of 0.01-0.10 m/s, immediately heating and treating for 24h in a steam atmosphere with the humidity of 1-100% after one layer of film is lifted by dipping, observing the change of the solution state to the gel state, and solidifying the solution to form a film; repeatedly operating for 1-10 times according to the step (2) to obtain a film with a certain thickness;
(3) firstly, taking out the film prepared in the step (2), soaking the film in alkaline liquor with the volume molar concentration of 1M at the temperature of 80 ℃ for 12 hours, and fully washing phosphoric acid in the film; then, the film is placed in deionized water to be soaked for 0.1 to 24 hours at the temperature of 0 to 100 ℃, and residual impurities are washed away; finally, the film is dried for 12h in vacuum, and the polybenzimidazole-based porous polymer ion exchange membrane is prepared.
Further, in the step (1), the reagent for adjusting the pH value of the mixed solution is acetic acid, phosphoric acid, sulfuric acid or polyphosphoric acid.
Further, in the step (1), the steam atmosphere 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.
Further, in the step (3), the alkali liquor is one or more of ammonium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate.
Further, the porous polymer ion exchange membrane prepared in the step (3) has the aperture size of 0.05-100 nm, the porosity of 1-200% and the thickness of 10-500 μm.
The application of the polybenzimidazole-based porous polymer ion exchange membrane or the polybenzimidazole-based porous polymer ion exchange membrane prepared by adopting a sol-gel preparation method in an alkaline water electrolysis bath comprises the following steps:
(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%;
(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 testing in immersionIn the anolyte and catholyte solutions, the polarization curves were obtained by measuring the cell voltage at different current densities, and were 50 ℃ at 200 mA-cm-2The durability thereof was evaluated at a constant current.
Further, the alkali liquor 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; 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 an alkaline water electrolysis bath, 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 the factors of the viscosity, the pulling speed, the concentration, the PH, the temperature, the steam atmosphere, the membrane forming time, the humidity and the like of the solution, the ion permeation selectivity of the membrane is improved after the alkali liquor is doped, and the porous polymer ion exchange membrane can be applied to the alkaline water electrolysis bath, so that 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 sol-gel, the prepared porous membrane is a spongy compact membrane, the liquid holding capacity is very high, 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 ion exchange 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 graph of the mechanical properties of the porous polymer ion-exchange membrane prepared in example 1.
FIG. 2 is a polarization curve of the porous polymer ion-exchange membranes prepared in examples 1, 2, 3 on an alkaline water electrolyzer.
FIG. 3 is a stability test of the porous polymer ion-exchange membrane prepared in example 1 in 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 adopting a sol-gel method comprises the following steps:
1. preparation of a stable solution.
Isophthalic acid (6.230g) and biphenyltetramine (8.037g) were dissolved in 300g of PPA, the pH of the solution was adjusted to 1 to obtain a stable, transparent solution, which was stirred well at a temperature of 110 ℃ and then polymerized for 24 hours at 250 ℃;
2. the porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 50% for 24h after each layer of film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare the polymer membrane with the porous structure.
3. And assembling the alkaline water electrolyzer by using the prepared porous membrane.
The method comprises the following steps:
(1) immersing the prepared porous polymer film into 25 wt% potassium hydroxide solution at 80 ℃ for 36 h;
(2) an alkali-doped porous polymer electrolyte membrane is applied to an alkaline water electrolyzer unit.
The anode and cathode are prepared by a Catalyst Coated Substrate (CCS) process. The anode catalyst is IrO2The cathode is a Pt/C plated titanium plate, the nickel plate is a bipolar plate, and the effective area of the membrane is 5cm2The water electrolysis apparatus is assembled by sandwiching the membrane electrode between the cathode and the anode. A gold plated porous Ti plate was used as the current collector in the cathode. Electrochemical testing was performed at 50 ℃, 25 wt% potassium hydroxide electrolyte, polarization curves were obtained by measuring cell voltage at different current densities, and at 50 ℃,200 mA · cm-2The durability was evaluated at a constant current density.
Example two
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a sol-gel method comprises the following steps:
1. the procedure for the preparation of the stabilized solution corresponds to the examples.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 60% for 24h after each layer of film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing away residual impurities, and drying in vacuum for 12h to finally prepare a polymer membrane with a porous structure;
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 sol-gel method comprises the following steps:
1. the procedure for the preparation of the stabilized solution corresponds to the example.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 70% for 24h after each layer of film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing away residual impurities, and drying in vacuum for 12h to finally prepare a polymer membrane with a porous structure;
3. the steps of assembling the alkaline water electrolyzer by using the prepared porous membrane are the same as the embodiment.
Example four
A preparation method of a polybenzimidazole-based porous polymer ion exchange membrane prepared by a sol-gel method comprises the following steps:
1. the procedure for the preparation of the stabilized solution corresponds to the example.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 80% for 24h after each layer of film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing away residual impurities, and drying in vacuum for 12h to finally prepare a polymer membrane with a porous structure;
3. the steps of assembling the alkaline water electrolyzer by using the prepared porous membrane are the same as the embodiment.
EXAMPLE five
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a sol-gel method comprises the following steps:
1. the procedure for the preparation of the stabilized solution corresponds to the example.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 90% for 24h after each layer of film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing away residual impurities, and drying in vacuum for 12h to finally prepare a polymer membrane with a porous structure;
3. the steps of assembling the alkaline water electrolyzer by using the prepared porous membrane are the same as the embodiment.
EXAMPLE six
A method for preparing a polybenzimidazole-based porous polymer ion exchange membrane by adopting a sol-gel method comprises the following steps:
1. the procedure for the preparation of the stabilized solution corresponds to the example.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a sol-gel method. The method comprises the following steps: slowly immersing the cleaned 20 x 20cm glass plate into a solution with the temperature of 250 ℃ after polymerization, standing for 10min, vertically and upwards pulling the glass plate at the speed of 0.05m/s, immediately carrying out heat treatment in a steam atmosphere with the humidity of 100% for 24h after each film is dipped and pulled, curing to form a film, and repeating for 5 times to obtain the film with a certain thickness. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing away residual impurities, and drying in vacuum for 12h to finally prepare a polymer membrane with a porous structure;
3. the steps of assembling the alkaline water electrolyzer by using the prepared porous membrane are the same as the embodiment.
EXAMPLE seven
A preparation method of a polybenzimidazole-based porous polymer ion exchange membrane prepared by a sol-gel method comprises the following steps:
1. the preparation steps of the stable solution are as follows:
dissolving 1, 5-anthracenedicarboxylic acid (2.66g) and biphenyltetramine (2.14g) in 100g of PPA, adjusting the pH of the solution to 1 to obtain a stable and transparent solution, sufficiently stirring at a temperature of 110 ℃, and then carrying out polymerization at 250 ℃ for 24 hours;
2. preparing the porous polybenzimidazole polymer ion exchange membrane by a sol-gel method. The steps are in accordance with the embodiments
3. The steps of assembling the alkaline water electrolyzer by using the prepared porous membrane are the same as the embodiment.
Example eight
The difference from the seventh example is that in the specific step of preparing the porous polybenzimidazole polymer membrane by the sol-gel method, a 20 × 20cm cleaned glass plate is slowly immersed into the solution at the temperature of 250 ℃ after polymerization, the solution is kept still for 10min, the glass plate is vertically and upwardly pulled at the speed of 0.05m/s, the film is thermally treated in a steam atmosphere with the humidity of 60% for 24h to be cured into a membrane after one membrane is immersed and pulled, and the membrane with a certain thickness is obtained after 5 times of repeated operation. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare porous polymer membranes with different types.
Example nine
The difference from the seventh example is that in the specific step of preparing the porous polybenzimidazole polymer membrane by the sol-gel method, a 20 × 20cm cleaned glass plate is slowly immersed into the solution at the temperature of 250 ℃ after polymerization, the solution is kept still for 10min, the glass plate is vertically and upwardly pulled at the speed of 0.05m/s, the film is thermally treated in a steam atmosphere with the humidity of 70% for 24h to be cured into a membrane after one membrane is immersed and pulled, and the membrane with a certain thickness is obtained after 5 times of repeated operation. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare porous polymer membranes with different types.
Example ten
The difference from the seventh example is that in the specific step of preparing the porous polybenzimidazole polymer membrane by the sol-gel method, a 20 × 20cm cleaned glass plate is slowly immersed into the solution at the temperature of 250 ℃ after polymerization, the solution is kept stand for 10min, the glass plate is vertically and upwardly pulled at the speed of 0.05m/s, the film is thermally treated in a steam atmosphere with the humidity of 80% for 24h to be cured into a membrane after one membrane is immersed and pulled, and the membrane with a certain thickness is obtained after 5 times of repeated operation. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare porous polymer membranes with different types.
EXAMPLE eleven
The difference from the seventh example is that in the specific step of preparing the porous polybenzimidazole polymer membrane by the sol-gel method, a 20 × 20cm cleaned glass plate is slowly immersed into the solution at the temperature of 250 ℃ after polymerization, the solution is kept still for 10min, the glass plate is vertically and upwardly pulled at the speed of 0.05m/s, the film is thermally treated in a steam atmosphere with the humidity of 90% for 24h to be cured into a membrane after one membrane is immersed and pulled, and the membrane with a certain thickness is obtained after 5 times of repeated operation. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare porous polymer membranes with different types.
Example twelve
The difference from the seventh example is that in the specific step of preparing the porous polybenzimidazole polymer membrane by the sol-gel method, a 20 × 20cm cleaned glass plate is slowly immersed into the solution at the temperature of 250 ℃ after polymerization, the solution is kept still for 10min, the glass plate is vertically and upwardly pulled at the speed of 0.05m/s, the film is thermally treated in the steam atmosphere with the humidity of 100% for 24h to be cured into a membrane after one membrane is immersed and pulled, and the membrane with a certain thickness is obtained after 5 times of repeated operation. Soaking the membrane in 1M ammonium hydroxide at 80 ℃ for 12h, fully washing phosphoric acid in the membrane, then placing the membrane in deionized water at 50 ℃ for 12h, washing residual impurities, and drying in vacuum for 12h to finally prepare porous polymer membranes with different types.
Comparative example
This example of a process for the preparation of a compact polybenzimidazole-based polymer comprising the following steps:
1. preparation of a homogeneous film-forming solution.
The method comprises the following steps: polybenzimidazole was dissolved in DMAc at room temperature and stirred for 1 hour to prepare a 12.5 wt% uniform transparent casting solution.
2. The porous polybenzimidazole polymer electrolyte membrane is prepared by a 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 dried at room temperature for 24 hours and then dried under vacuum at 80 ℃ for 12 hours.
3. The steps of the alkaline water electrolyzer assembled by the prepared membrane are consistent with the embodiment.
In summary, the comparison table of the properties of the porous polymer ion exchange membranes prepared in all the examples is shown below.
Figure BDA0002660680570000101
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 (7)

1. The application of a porous polymer ion exchange membrane based on polybenzimidazole is characterized in that: for use in alkaline water electrolysers;
the preparation method of the polybenzimidazole-based porous polymer ion exchange membrane comprises the following steps:
(1) firstly, dissolving diacid with a-R-structure and biphenyltetramine in polyphosphoric acid, wherein the concentration of an organic high molecular polymer in a mixed solution is 1-70 wt%; then, adjusting the pH value of the mixed solution to 1-7 to obtain a stable and transparent mixed solution; finally, fully stirring the mixed solution at the temperature of 5-300 ℃ for 0.5-24 h, and carrying out polymerization reaction;
(2) adjusting the temperature of the solution after the polymerization reaction in the step (1) to 190-300 ℃, then slowly immersing the cleaned substrate into the solution after the polymerization reaction, standing for 0.5-30 min, vertically lifting the substrate upwards at the speed of 0.01-0.10 m/s, immediately heating and treating for 24h in a steam atmosphere with the humidity of 50-100% after one layer of film is lifted by dipping, observing the change of the solution state to the gel state, and solidifying the solution to form a film; repeatedly operating for 1-10 times according to the step (2) to obtain a film with a certain thickness;
(3) firstly, taking out the film prepared in the step (2), soaking the film in alkaline liquor with the volume molar concentration of 1M at the temperature of 80 ℃ for 12 hours, and fully washing phosphoric acid in the film; then, the film is placed in deionized water to be soaked for 0.1 to 24 hours at the temperature of 0 to 100 ℃, and residual impurities are washed away; finally, the film is dried for 12 hours in vacuum to prepare a porous polymer ion exchange membrane based on polybenzimidazole;
the chemical structural general formula of the polybenzimidazole-based porous polymer ion exchange membrane is as follows:
Figure FDA0003485459580000011
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 FDA0003485459580000021
2. use according to claim 1, characterized in that: in the step (1), the reagent for adjusting the pH value of the mixed solution is acetic acid, phosphoric acid, sulfuric acid or polyphosphoric acid.
3. Use according to claim 1, characterized in that: in the step (1), the steam atmosphere 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.
4. Use according to claim 1, characterized in that: in the step (3), the alkali liquor is one or more of ammonium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate.
5. Use according to claim 1, characterized in that: the porous polymer ion exchange membrane prepared in the step (3) has the aperture size of 0.05-100 nm, the porosity of 1-200% and the thickness of 10-500 mu m.
6. Use according to claim 1, characterized in that it comprises the following steps:
(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%;
(2) and (2) installing the alkali-doped porous polymer ion exchange membrane prepared in the step (1) in an alkaline water electrolyzer device.
7. Use according to claim 6, characterized in that: the alkali liquor 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; 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.
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