Polyaryl-piperidine polymer electrolyte membrane, preparation method and application

Abstract

The invention belongs to the technical field of high-molecular polymer membrane materials, and discloses a polyaryl-piperidine polymer electrolyte membrane, and a preparation method and application thereof. The raw materials comprise an aryl monomer and 1-benzyl-4-piperidinecarboxaldehyde, or the aryl monomer, the 1-benzyl-4-piperidinecarboxaldehyde and a branching agent. A benzyl-containing piperidinium molecular framework is designed, a piperidine ring is connected with a main chain through a flexible spacer, meanwhile, benzyl is connected to an N atom, and the benzyl has large steric hindrance, so that the stability of AEM under an alkaline condition, especially under a high-temperature and high-concentration severe condition, is effectively relieved. Branching agents such as triphenylbenzene are added into a main chain structure to enhance the mechanical property and alkali-resistant stability of the main chain structure, and the polymer electrolyte membrane with high conductivity, high mechanical property and high alkali resistance is prepared by adopting a simple solution casting method and is applied to AEMWE.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular polymer film materials, and particularly relates to a polyaryl-piperidine polymer electrolyte film, a preparation method and application. BACKGROUND

[0002] Hydrogen energy, as a global energy transformation and carbon neutralization implementation carrier, its green preparation technology has been widely concerned. Water electrolysis can convert water into hydrogen by using renewable energy (such as solar energy and wind energy), and store chemical energy, which can not only improve the utilization efficiency of intermittent energy, but also achieve nearly zero carbon emission in the whole chain, and is the core path to truly realize green hydrogen production. Among various electrolysis technologies, proton exchange membrane water electrolysis (PEMWE) has been commercialized, and has advantages of fast response speed and high hydrogen purity, but it relies on platinum group noble metal catalyst and high-cost components, which limits its large-scale application.

[0003] Compared with the above, anion exchange membrane water electrolysis (AEMWE) shows significant cost potential: on the one hand, it allows the use of non-noble metal catalysts, which greatly reduces the cost of basic materials; on the other hand, due to the higher pH environment, the anion exchange membrane (AEM) significantly improves the oxygen reduction reaction (ORR) kinetics, and can replace the expensive proton exchange membrane. In the system, AEM acts as a medium for rapid conduction and a barrier to prevent gas crossover, and its performance directly determines the efficiency and service life of the electrolyzer. However, the long-term chemical stability of AEM in strong alkaline conditions is still a technical problem to be solved, and traditional methods such as copolymerization, crosslinking and branching cannot fundamentally solve the problem. Therefore, it is necessary to develop a new type of anion exchange membrane that can maintain high ionic conductivity and mechanical strength while slowing down the degradation of the membrane material in alkaline environment. - The fast conducting medium and the barrier to prevent gas crossover, and its performance directly determines the efficiency and service life of the electrolyzer. However, the long-term chemical stability of AEM in strong alkaline conditions is still a technical problem to be solved, and traditional methods such as copolymerization, crosslinking and branching cannot fundamentally solve the problem. Therefore, it is necessary to develop a new type of anion exchange membrane that can maintain high ionic conductivity and mechanical strength while slowing down the degradation of the membrane material in alkaline environment.

[0004] Traditional polytriphenylphosphine piperidine (PTP) solves the problem of alkaline stability of traditional aryl ether chain by using ether bond-free rigid skeleton (such as triphenyl highly aromatic). For example, the PiperION series of anion exchange membranes developed by the American Versogen company use a chemical structure of functionalized poly(aryl piperidine) resin material mainly composed of aromatic rings. The PiperION anion exchange membrane shows excellent ion conductivity and chemical stability, and can work in acidic or corrosive environments. However, the molecular design of the direct bonding of the piperidine ring and the main chain of PiperION anion exchange membrane causes irreconcilable structural contradictions. For example, the rigid triphenyl main chain forces the piperidine ring to deviate from the ideal chair conformation, causing the ring tension to increase sharply, and the β-hydrogen existing in the traditional piperidine ring is prone to Hofmann elimination in alkaline environment. The above problems significantly reduce the Hofmann elimination reaction energy barrier, causing the piperidine onium skeleton to be easily degraded irreversibly in alkaline environment. SUMMARY

[0005] In view of the existing problems of PTP, the application provides a polyaryl-piperidine polymer electrolyte membrane, a preparation method and application, a benzyl-containing piperidinium molecular architecture is designed, a flexible spacer is used to connect the piperidine ring and the main chain, and a benzyl group is connected to the N atom, the benzyl group has large steric hindrance, and the stability of the AEM under alkaline conditions, especially under harsh conditions of high temperature and high concentration, is effectively relieved. The application initiates the benzyl piperidinium molecular architecture: the main chain and the piperidine ring are connected through a flexible alkyl spacer, and the quaternary ammonium group is connected with the benzyl group. The design achieves a double breakthrough: the N-benzyl piperidine quaternary ammonium salt can inhibit Hofmann elimination and promote microphase separation, and the piperidine ring is suspended to release its conformation, thereby fundamentally blocking the Hofmann elimination path. The application uses aryl monomers and 1-benzyl-4-piperidine formaldehyde as starting materials, synthesizes a homopolymer, and uses triphenylbenzene and 2,4,6-triphenyl-1,3,5-triazine as branching reagents, and through super acid electrophilic reaction, polymers with different branching degrees are obtained, and finally the above polymer membrane is applied to AEMWE. The prepared polymer electrolyte membrane is a uniform transparent and dense membrane material.

[0006] The application adopts the following technical scheme: a polyaryl-piperidine polymer electrolyte membrane, raw material substances are aryl monomers and 1-benzyl-4-piperidine formaldehyde, or aryl monomers, 1-benzyl-4-piperidine formaldehyde and a branching agent.

[0007] When the raw material substances are aryl monomers and 1-benzyl-4-piperidine formaldehyde, the molar ratio of the aryl monomers to the 1-benzyl-4-piperidine formaldehyde is 1:(1-1.3); when the raw material substances are aryl monomers, 1-benzyl-4-piperidine formaldehyde and a branching agent, the molar ratio of (aryl monomers + branching agent) to 1-benzyl-4-piperidine formaldehyde is 1:(1-1.3).

[0008] The aryl monomer is one or two of formula 1 to formula 15; The branching agent is one of formula 16 to formula 27:

[0009] A preparation method of a polyaryl-piperidine polymer electrolyte membrane, comprising the following steps: Step 1: mixing of raw material substances; Step 1.1, dissolving aryl monomers and 1-benzyl-4-piperidine formaldehyde, or aryl monomers, 1-benzyl-4-piperidine formaldehyde and a branching agent in dichloromethane, and performing mechanical stirring to obtain a mixed solution; Step 1.2, adding a catalyst into the mixed solution to perform a reaction, and obtaining a post-reaction solution; Step 2: precipitation of the reactants; ​​The reaction solution obtained in step 1.2 is added with a precipitant to obtain a filamentous solid precipitate or a powdery precipitate; the filamentous solid precipitate or the powdery precipitate is washed with the precipitant and deionized water alternately until neutral; drying, crushing, and obtaining a polymer material; Step 3: Quaternization of the polymer; Step 3.1, the polymer material is dissolved in an organic solvent at room temperature, and electromagnetic stirring is performed until the solution is uniform, obtaining a polymer solution; a quaternization reagent is added, and the solution is reacted in the dark for 48-96 hours; Step 3.2, the solution after the dark reaction in step 3.1 is precipitated in a purification reagent, and washed with deionized water multiple times, and dried to obtain a quaternized polymer material; Step 3.3, the quaternized polymer material is dissolved in an organic solvent at room temperature, and electromagnetic stirring is performed until the solution is uniform, obtaining a quaternized polymer solution; Step 3.4, the quaternized polymer solution is prepared into a film material by a solution casting method, specifically, the quaternized polymer solution in step 3.3 is dried and volatilized on a culture dish to obtain a polymer electrolyte film; Step 4: Ion exchange; After the polymer electrolyte film obtained in step 3.4 is taken out, it is soaked in an exchange solution for 48-96 hours to replace the counterions therein, obtaining a polyaryl-piperidine polymer electrolyte film.

[0010] The mass ratio of the raw material substance to dichloromethane in step 1.1 is 5%-10%; the mechanical stirring in step 1.1 is performed under ice bath or room temperature.

[0011] In step 1.2, the catalyst is triflic acid or methane sulfonic acid and triflic acid; when the catalyst contains methane sulfonic acid, the volume ratio of methane sulfonic acid to the catalyst is not more than 6%; the addition amount of the catalyst accounts for more than or equal to 40% and less than 90% of the total volume of the catalyst and dichloromethane; the reaction in step 1.2 is performed under stirring, and after reacting for 10-40 minutes under ice bath, the reaction is continued at room temperature for 0-168 hours.

[0012] In step 1, the reaction occurs as shown below: or In the above reaction, R1 and R2 in the aryl monomer are any group in formula 1-15, and B is any branching agent in formula 16-27.

[0013] The precipitant in step 2 is one or more of sodium bicarbonate solution, sodium carbonate solution, potassium carbonate solution, and sodium hydroxide solution; the concentration of the precipitant is 1 mol / L-2 mol / L; the volume ratio of the total amount of solution added after the reaction to the total amount of precipitant is 1:(50-100); in step 2, the drying temperature is 80℃-100℃, and the drying time is 8h-12h.

[0014] In step 3.1, the organic solvent is one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the mass ratio of the polymer material to the polar organic solvent is 1:(50-100); the quaternizing agent is iodomethane, potassium iodide, and K2CO3; and the quaternization conditions are a reaction at room temperature in the dark for 48-96 hours. In step 3.4, the drying temperature is 80℃-120℃ and the drying time is 24-36h.

[0015] The prepared polyaryl-piperidine polymer electrolyte membrane has a conductivity of 60 mS·cm at 80 °C. -1 -200mS·cm -1 The tensile strength at room temperature is 15.0 MPa-35.0 MPa.

[0016] The polyaryl-piperidine polymer electrolyte membrane can be used in water electrolysis.

[0017] By adding branching agents such as triphenylbenzene to the main chain structure to enhance its mechanical properties and alkali resistance, a polymer electrolyte membrane with high conductivity, high mechanical properties and high alkali resistance was prepared by a simple solution casting method and applied to AEMWE.

[0018] The beneficial effects of this invention are as follows: 1. The polyaryl-piperidine polymer electrolyte membrane prepared by this invention contains an aromatic backbone in its main chain, and has good mechanical properties and stability; 2. In this invention, the piperidine ring is connected to the aryl main chain by a flexible alkyl spacer group, and the suspended design liberates the conformation of the piperidine ring; 3. In this invention, the quaternary ammonium N in the piperidine ring is linked to a benzyl group. The benzyl group is large in volume and the aromatic ring is highly rigid, thereby minimizing the possibility of elimination reactions. 4. This invention significantly improves the mechanical properties and alkali resistance of polyaryl-piperidine polymer electrolyte membranes by adding branching agents such as triphenylbenzene to the biphenyl skeleton. 5. The materials used in this invention are readily available, inexpensive, and the reaction conditions are mild. Attached Figure Description

[0019] Figure 1The 1H NMR spectrum of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1; Figure 2 The 1H NMR spectrum of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1 after immersion in 5M KOH for 6 days shows its degradation. Figure 3 The 1H NMR spectrum of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1 after immersion in 5M KOH for 12 days shows its degradation. Figure 4 The proton NMR spectrum of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1 after immersion in 10M KOH for 6 days is a result of its degradation. Figure 5 The proton NMR spectrum of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1 after being immersed in 10M KOH for 12 days for degradation. Figure 6 The conductivity curve of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1 is shown. Figure 7 The conductivity curve of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 2 is shown. Figure 8 The figure shows the tensile strength curve of the polyaryl-piperidine polymer electrolyte membrane obtained in Example 1. The horizontal axis represents different elongation at break (%), and the vertical axis represents tensile stress (MPa).

[0020] Figure 9 The figure shows the tensile strength curve of the polyaryl-piperidine polymer electrolyte membrane obtained in Comparative Example 1. The horizontal axis represents different elongation at break (%), and the vertical axis represents tensile stress (MPa).

[0021] Figure 10 The figure shows the tensile strength curve of the polyaryl-piperidine polymer electrolyte membrane obtained in Comparative Example 2. The horizontal axis represents different elongation at break (%), and the vertical axis represents tensile stress (MPa). Detailed Implementation

[0022] The invention will now be described in detail with specific examples.

[0023] Example 1; The steps for preparing the biphenyl-1-benzyl-4-piperidine carboxaldehyde composite membrane are as follows: R1 and R2 are selected from aryl monomers of type 1, and the polymerization procedure is as follows: (1) First, biphenyl and 1-benzyl-4-piperidinecarboxaldehyde are mixed and dissolved in dichloromethane solvent (5 ml) to form a reaction solution with a molar ratio of biphenyl:1-benzyl-4-piperidinecarboxaldehyde=1:1.1 and a branching agent monomer content of 0. The reaction solution is mechanically stirred evenly under ice bath conditions, and trifluoromethanesulfonic acid (2 ml) is added. The reaction is continued until viscosity is reached. (2) The viscous product was poured into a 1M NaHCO3 solution for precipitation and soaking, crushed and soaked in NaHCO3 solution again, rinsed with a large amount of deionized water until neutral, and dried in an 80℃ constant temperature oven for 12h to obtain the corresponding polymer material. (3) At room temperature, the polymer material was dissolved in the organic solvent N-methylpyrrolidone (15 mL), and the solution was stirred evenly with electromagnetic stirring to obtain a polymer solution; then iodomethane (1 mL), potassium iodide and K2CO3 were added, and the reaction was carried out in the dark for 48 h. (4) The obtained solution was precipitated in ethyl acetate, a purification reagent, and washed repeatedly with deionized water and dried to obtain the quaternized polymer material; (5) Under normal temperature conditions, a certain mass of quaternized polymer material is weighed and dissolved in N-methylpyrrolidone to obtain a quaternized polymer solution with a mass fraction of 2%. After obtaining a homogeneous solution by electromagnetic stirring, it is poured into a clean petri dish and the solvent is evaporated at 80°C. The film formation time is 24h-36h. After the solvent has completely evaporated, the polymer electrolyte membrane is obtained. (6) The above polymer electrolyte membrane was completely immersed in the 1M NaCl exchange solution for 48 hours to replace the counterion I. - The resulting polymer electrolyte membrane exhibits excellent proton conductivity and mechanical properties.

[0024] Example 2; The steps for preparing the dibenzothiophene-biphenyl-1-benzyl-4-piperidinecarboxaldehyde composite membrane are as follows: R1 is selected from aryl monomer type 1, and R2 is selected from aryl monomer type 8. The polymerization procedure is as follows: (1) First, dibenzothiophene, biphenyl and 1-benzyl-4-piperidinecarboxaldehyde are mixed and dissolved in dichloromethane solvent (5 ml) to form a reaction solution with a molar ratio of dibenzothiophene: biphenyl: 1-benzyl-4-piperidinecarboxaldehyde = 0.3: 0.7: 1.1 and the content of branching agent monomer is 0. The reaction solution is mechanically stirred evenly under ice bath conditions, and trifluoromethanesulfonic acid (2 ml) is added. After 5 min, the ice bath is removed and the reaction continues for 10 min until viscosity appears. (2) The viscous product was poured into a 1M NaHCO3 solution for precipitation and soaking, crushed and soaked in NaHCO3 solution again, rinsed with a large amount of deionized water until neutral, and dried in an 80℃ constant temperature oven for 12h to obtain the corresponding polymer material. (3) At room temperature, the polymer material was dissolved in the organic solvent N-methylpyrrolidone (15 mL), and the solution was stirred evenly with electromagnetic stirring to obtain a polymer solution; then iodomethane (1 mL), potassium iodide and K2CO3 were added, and the reaction was carried out in the dark for 48 h. (4) The obtained solution was precipitated in ethyl acetate, a purification reagent, and washed repeatedly with deionized water and dried to obtain the quaternized polymer material; (5) Under normal temperature conditions, a certain mass of quaternized polymer is weighed and dissolved in N-methylpyrrolidone to obtain a quaternized polymer solution with a mass fraction of 2%. After obtaining a homogeneous solution by electromagnetic stirring, it is poured into a clean petri dish and the solvent is evaporated at 80°C. The film formation time is 24h-36h. After the solvent has completely evaporated, the polymer electrolyte membrane is obtained. (6) The above polymer electrolyte membrane was completely immersed in the 1M NaCl exchange solution for 48 hours to replace the counterion I. - The resulting polymer electrolyte membrane exhibits excellent proton conductivity and mechanical properties.

[0025] Example 3; The steps for preparing the dibenzothiophene-biphenyl-1-benzyl-4-piperidinecarboxaldehyde triphenylbenzene branched composite membrane are as follows: R1 is selected from aryl monomer type 1, R2 is selected from aryl monomer type 8, and the branching agent is selected from branching agent type 18. The polymerization procedure is as follows: (1) First, dibenzothiophene, biphenyl, 1-benzyl-4-piperidinecarboxaldehyde and triphenylbenzene are mixed and dissolved in dichloromethane solvent (5 ml) to form a reaction solution with a molar ratio of dibenzothiophene: biphenyl: triphenylbenzene: 1-benzyl-4-piperidinecarboxaldehyde = 0.3: 0.63: 0.07: 1.1. The reaction solution is mechanically stirred evenly under ice bath conditions, and trifluoromethanesulfonic acid (2 ml) is added. After 5 min, the ice bath is removed, and the reaction continues for 10 min until viscosity appears. (2) The viscous product was poured into a 1M NaHCO3 solution for precipitation and soaking, crushed and soaked in NaHCO3 solution again, rinsed with a large amount of deionized water until neutral, and dried in an 80℃ constant temperature oven for 12h to obtain the corresponding polymer material. (3) At room temperature, the polymer material was dissolved in the organic solvent N-methylpyrrolidone (15 mL), and the solution was stirred evenly with electromagnetic stirring to obtain a polymer solution; then iodomethane (1 mL), potassium iodide and K2CO3 were added, and the reaction was carried out in the dark for 48 h. (4) The obtained solution was precipitated in ethyl acetate, a purification reagent, and washed repeatedly with deionized water and dried to obtain the polymer material; (5) Under normal temperature conditions, a certain mass of quaternized polymer is weighed and dissolved in N-methylpyrrolidone to obtain a quaternized polymer solution with a mass fraction of 2%. After obtaining a homogeneous solution by electromagnetic stirring, it is poured into a clean petri dish and the solvent is evaporated at 80°C. The film formation time is 24h-36h. After the solvent has completely evaporated, the polymer electrolyte membrane is obtained.

[0026] (6) The above polymer electrolyte membrane was completely immersed in the 1M NaCl exchange solution for 48 hours to replace the counterion I. - The obtained polymer electrolyte membrane has a conductivity of 120 mS·cm at 80℃. -1 The tensile strength at room temperature is 23.21 MPa.

[0027] Comparative Example 1; (1) First, mix p-terphenyl and N-methyl-4-piperidinone and dissolve them in dichloromethane solvent (5 ml) to form a reaction solution with a molar ratio of p-terphenyl:N-methyl-4-piperidinone = 1:1.1 and a branching agent monomer content of 0. The reaction solution is mechanically stirred evenly under ice bath conditions, and trifluoromethanesulfonic acid (2 ml) is added. The reaction is continued until viscosity is reached. (2) The viscous product was poured into a 1M NaHCO3 solution for precipitation and soaking, crushed and soaked in NaHCO3 solution again, rinsed with a large amount of deionized water until neutral, and dried in an 80℃ constant temperature oven for 12h to obtain the corresponding polymer. (3) At room temperature, the polymer material was dissolved in the organic solvent N-methylpyrrolidone (15 mL), and the mixture was stirred electromagnetically until homogeneous to obtain a polymer solution; then iodomethane (1 mL), potassium iodide and K2CO3 were added, and the reaction was carried out in the dark for 48 h. (4) The obtained solution was precipitated in ethyl acetate, a purification reagent, and washed repeatedly with deionized water and dried to obtain the quaternized polymer material; (5) Under normal temperature conditions, a certain mass of quaternized polymer material is weighed and dissolved in N-methylpyrrolidone to obtain a quaternized polymer solution with a mass fraction of 2%. After obtaining a homogeneous solution by electromagnetic stirring, it is poured into a clean petri dish and the solvent is evaporated at 80°C. The film formation time is 24-36h. After the solvent has completely evaporated, the polymer electrolyte membrane is obtained. (6) The above polymer electrolyte membrane was completely immersed in the 1M NaCl exchange solution for 48 hours to replace the counterion I. - .

[0028] Comparative Example 2; (1) First, biphenyl and N-methyl-piperidine-4-carboxaldehyde are mixed and dissolved in dichloromethane solvent (5 ml) to form a reaction solution with a molar ratio of biphenyl:N-methyl-piperidine-4-carboxaldehyde = 1:1.1 and the content of branching agent monomer is 0. The reaction solution is mechanically stirred evenly under ice bath conditions, and trifluoromethanesulfonic acid (2 ml) is added. The reaction is continued until viscosity is reached. (2) The viscous product was poured into a 1M NaHCO3 solution for precipitation and soaking, crushed and soaked in NaHCO3 solution again, rinsed with a large amount of deionized water until neutral, and dried in an 80℃ constant temperature oven for 12h to obtain the corresponding polymer. (3) At room temperature, the polymer material was dissolved in the organic solvent N-methylpyrrolidone (15 mL), and the solution was stirred evenly with electromagnetic stirring to obtain a polymer solution; then iodomethane (1 mL), potassium iodide and K2CO3 were added, and the reaction was carried out in the dark for 48 h. (4) The obtained solution was precipitated in ethyl acetate, a purification reagent, and washed repeatedly with deionized water and dried to obtain the quaternized polymer material; (5) Under normal temperature conditions, a certain mass of quaternized polymer is weighed and dissolved in N-methylpyrrolidone to obtain a quaternized polymer solution with a mass fraction of 2%. After obtaining a homogeneous solution by electromagnetic stirring, it is poured into a clean petri dish and the solvent is evaporated at 80°C. The film formation time is 24h-36h. After the solvent has completely evaporated, the polymer electrolyte membrane is obtained. (6) The above polymer electrolyte membrane was completely immersed in the 1M NaCl exchange solution for 48 hours to replace the counterion I. - .

Claims

1. A polyaryl-piperidine polymer electrolyte film, characterized by, The raw material of the polyaryl-piperidine polymer electrolyte film is an aryl monomer and 1-benzyl-4-piperidine formaldehyde, or an aryl monomer, 1-benzyl-4-piperidine formaldehyde and a branching agent; when the raw material is an aryl monomer and 1-benzyl-4-piperidine formaldehyde, the molar ratio of the aryl monomer to 1-benzyl-4-piperidine formaldehyde is 1:(1-1.3); when the raw material is an aryl monomer, 1-benzyl-4-piperidine formaldehyde and a branching agent, the molar ratio of (aryl monomer + branching agent) to 1-benzyl-4-piperidine formaldehyde is 1:(1-1.3).

2. The poly(aryl-piperidine) polymer electrolyte film according to claim 1, wherein The aryl monomer is one or two of formulas 1-15; ； The branching agent is one of formulas 16-27: 。 3. A method for producing the poly(aryl-piperidine) polymer electrolyte film according to any one of claims 1 to 2, characterized by, The method comprises the following steps: Step 1: mixing of raw materials; Step 1.1, dissolving the aryl monomer and 1-benzyl-4-piperidine formaldehyde, or the aryl monomer, 1-benzyl-4-piperidine formaldehyde and the branching agent in dichloromethane, and mechanically stirring to obtain a mixed solution; Step 1.2, adding a catalyst to the mixed solution to react and obtain a post-reaction solution; Step 2: precipitation of the reactants; adding a precipitant to the post-reaction solution obtained in step 1.2 to obtain a filamentous solid precipitate or a powdery precipitate; washing the filamentous solid precipitate or the powdery precipitate with the precipitant and deionized water alternately until neutral; drying, crushing and obtaining a polymer material; Step 3: quaternization of the polymer; Step 3.1, dissolving the polymer material in an organic solvent at room temperature, and electromagnetically stirring until uniform to obtain a polymer solution; adding a quaternization reagent and avoiding light for 48-96 hours; Step 3.2, precipitating the solution after the light-avoiding reaction in step 3.1 in a purification reagent, washing with deionized water for multiple times, and drying to obtain a quaternized polymer material; Step 3.3, dissolving the quaternized polymer material in an organic solvent at room temperature, and electromagnetically stirring until uniform to obtain a quaternized polymer solution; Step 3.4, preparing a film material by solution casting of the quaternized polymer solution, specifically, drying and volatilizing the quaternized polymer solution in step 3.3 on a culture dish to obtain a polymer electrolyte film; Step 4: ion exchange; after taking down the polymer electrolyte film obtained in step 3.4, soaking in an exchange solution for 48-96 hours to replace the counter ions therein, and obtaining a polyaryl-piperidine polymer electrolyte film.

4. The method for preparing a poly(aryl-piperidine) polymer electrolyte film according to claim 3, characterized by, The mass ratio of the raw materials to dichloromethane in step 1.1 is 5%-10%; the mechanical stirring in step 1.1 is performed under ice bath or at room temperature.

5. The method for preparing the polyaryl-piperidine polymer electrolyte membrane according to claim 3, characterized in that, In step 1.2, the catalyst is triflic acid or methane sulfonic acid and triflic acid; when the catalyst contains methane sulfonic acid, the volume ratio of methane sulfonic acid to the catalyst is not more than 6%; the addition amount of the catalyst accounts for more than or equal to 40% and less than 90% of the total volume of the catalyst and dichloromethane; the reaction in step 1.2 is performed under stirring, and after reacting for 10-40 minutes under ice bath, the reaction is continued for 0-168 hours at room temperature.

6. The method for preparing the polyaryl-piperidine polymer electrolyte membrane according to claim 3, characterized in that, In step 1, the reaction occurs as shown below: or In the above reaction, R1 and R2 in the aryl monomer are any of the groups in Formula 1-Formula 15, and B is any branching agent in Formula 16-Formula 27.

7. The method for preparing the polyaryl-piperidine polymer electrolyte membrane according to claim 3, characterized in that, The precipitant in the step 2 is one or more of sodium bicarbonate solution, sodium carbonate solution, potassium carbonate solution, and sodium hydroxide solution; the concentration of the precipitant is 1-2 mol / L; the total volume ratio of the post-reaction solution to the precipitant is 1: (50-100); in the step 2, the drying temperature is 80-100℃, and the drying time is 8-12 h.

8. The method for preparing the polyaryl-piperidine polymer electrolyte membrane according to claim 3, characterized in that, In the step 3.1, the organic solvent is one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the mass ratio of the polymer material to the polar organic solvent is 1: (50-100); the quaternization reagent is iodomethane, potassium iodide, and K2CO3, and the quaternization condition is room temperature, dark reaction for 48-96 h; In the step 3.4, the drying temperature is 80-120℃, and the drying time is 24-36 h.

9. The method for preparing the polyaryl-piperidine polymer electrolyte membrane according to claim 8, characterized in that, The prepared polyaryl-piperidine polymer electrolyte film has an electrical conductivity of 60 mS-cm at 80 °C -1 - 200 mS-cm -1 , and a tensile strength of 15.0-35.0 MPa at room temperature.

10. Use of a poly(arylene-piperidine) polymer electrolyte film, characterized in that The polyaryl-piperidine polymer electrolyte membrane is the polyaryl-piperidine polymer electrolyte membrane according to claim 1 or 2, or the polyaryl-piperidine polymer electrolyte membrane prepared by the preparation method according to any one of claims 3-9, and is applied in water electrolysis.

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