Random copolymer sulfonated polyphenylene benzimidazole material for fuel cells and method for preparing the same

Abstract

The application provides a random copolymer sulfonated benzene polyphenyl ionomer material and a preparation method thereof, and belongs to the technical field of proton exchange membrane materials of fuel cells, and aims to solve the technical problems of low conductivity and poor chemical stability of the proton exchange membrane. The ionomer is prepared from monomers I and II, is dissolved in a polar solvent reaction medium, a catalyst is added into the reaction system at 70-100 DEG C, and the reaction is continuously carried out for 3-6 hours under the condition; after the reaction is completed, the reaction liquid is poured into a concentrated hydrochloric acid aqueous solution, a precipitate is separated out and is filtered; then, the precipitate is washed with concentrated hydrochloric acid and deionized water, and finally is dried to obtain the target ionomer. The preparation method has the characteristics of simple synthesis, low cost, high molecular weight of the obtained polymer, good conductive performance of the proton exchange membrane, high water absorption and the like, and the prepared proton exchange membrane has a wide application prospect when used as the proton exchange membrane of a hydrogen fuel cell.

Description

Technical Field

[0001] This invention belongs to the technical field of proton exchange membrane materials for fuel cells, and particularly relates to an ionomer. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs) convert chemical energy into electrical energy. Due to their high conversion efficiency and fast start-up, they are widely used as clean and efficient energy conversion devices. Currently, perfluorosulfonic acid (PFSA) polymer membranes (such as Nafion and Gore Select) are most commonly used as electrolytes, exhibiting high proton conductivity and excellent mechanical properties. However, they also have some technical problems, such as high gas permeability, limited operating temperature, and complex manufacturing processes. To address the problems of PFSA-based proton exchange membranes, current research mainly focuses on improving existing PFSA-based proton exchange membranes and developing novel non-fluorinated proton exchange membrane materials. Sulfonated benzene-substituted polyphenylene oxide (PEM) has advantages such as good thermal stability and low gas permeability, and is expected to become a new type of proton exchange membrane material.

[0003] Ionomers are polymers containing ionic groups in their hydrocarbon molecular chains. These ionic groups can form cross-linked networks through ionic interactions, thus possessing many unique and excellent properties. Currently, sulfonated phenylene ionomer membrane materials are widely studied. Holdcroft et al. reported that sulfonated phenylene ionomers exhibit very high thermal oxidative stability and good dimensional stability. Miyatake successfully synthesized a series of novel sulfonated polyphenylene ionomers (SPP-BP) containing sulfonated p-phenylene and unsubstituted p-biphenylene and meta-biphenylene via Ni(O)-promoted coupling reactions. These SPP-BP membranes exhibit high proton conductivity, mechanical strength, and chemical stability. This preparation method is characterized by its simple synthesis, high molecular weight of the obtained ionomers, and ease of control. Patent publication number CN117304452A discloses a sulfonated polyphenylene ionomer, its preparation method, and a proton exchange membrane. The preparation method of the sulfonated polyphenylene ionomer involves dissolving the polymer in monomers I, II, and III in a solvent, and under alkaline conditions, promoting the coupling reaction between monomers through Ni(O) catalysis. The copolymer is then obtained through precipitation, separation, and drying. When used as an exchange membrane in a fuel cell, it exhibits high proton conductivity and low permeability. Although a series of sulfonated phenylene ionomers have been disclosed in the prior art, the influence of different ionomer structures on performance needs further exploration. Ionomer proton exchange membranes still suffer from problems such as low conductivity and poor chemical stability. Summary of the Invention

[0004] To address the technical problems of low conductivity and poor chemical stability of proton exchange membranes, this invention proposes a random copolymer sulfonated phenyl ionomer material and its preparation method. The proton exchange membrane material prepared by this ionomer exhibits high proton conductivity and high chemical stability.

[0005] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0006] A random copolymer sulfonated phenyl ionomer material for fuel cells, with the following structural formula:

[0007]

[0008] Where R is R1, R2, R3, R4, R5, and R6 are independently selected from H, F, and -(CF2), respectively. x At least one of CF3, -CF3 and phenyl, n1 is an integer from 0 to 10, n2 is an integer from 0 to 12, x is an integer from 0 to 15; m:n is 1:(0-99).

[0009] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps: mixing monomer I, monomer III, a catalyst, an alkaline regulator, and a solvent to obtain a reaction solution and performing a coupling reaction; after the reaction is completed, the target ionomer is obtained; the structural formulas of monomer I and monomer II are shown below:

[0010] Where X is Cl, Br, or I, and R is selected from:

[0011] One of them, R1, R2, R3, R4, R5, and R6, are independently selected from H, F, and -(CF2), respectively. x At least one of CF3, -CF3 and phenyl, where n1 is an integer from 0 to 10, n2 is an integer from 0 to 12, and x is an integer from 0 to 15.

[0012] The molar ratio of monomer I to monomer II is 1:(0-99); the concentration of monomer I in the reaction solution is 0.04-0.7 mmol / mL.

[0013] The solvent is any one of N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), or N-methylpyrrolidone (NMP).

[0014] The alkaline regulator is any one or more of K2CO3, Na2CO3, LiOH, NaOH or KOH; the molar ratio of monomer I to alkaline regulator is 1:(1-20).

[0015] The catalyst comprises a Ni(0) catalyst and a ligand, wherein the Ni(0) catalyst is one of Ni(COD)2, Ni(CDT), Ni(OAc)2, NiBr2 / Zn, NiCl2 / Zn, and NiI2 / Zn; the ligand is 2,2'-bipyridine, and the molar ratio of the sum of the moles of monomer I and monomer II to the molar ratio of the Ni(0) catalyst is 1:(1-6).

[0016] The molar ratio of Ni(0) to 2,2'-bipyridine is 1:(0.2-5).

[0017] The coupling reaction is carried out at a temperature of 50-100℃ for 2-24 hours.

[0018] After the reaction is complete, the reaction solution is added to the precipitant, the precipitate is filtered, and then the precipitate is washed and dried to obtain the target ionomer.

[0019] The precipitant is an acidic aqueous solution; the acidic aqueous solution is hydrochloric acid or sulfuric acid aqueous solution; the concentration of the acidic aqueous solution is 4-6 mol / L.

[0020] The beneficial effects of this invention are: the synthesis of this invention is simple and low-cost, the polymer obtained has a high molecular weight, good conductivity of the proton exchange membrane, and high water absorption. At the same time, this invention introduces alkyl chains or small molecule benzene ring segments (monomer II) on the basis of sulfonated benzene-substituted polyphenylene, which is mainly used to improve the mechanical properties of sulfonated benzene-substituted polyphenylene membrane materials. The proton exchange membrane prepared has broad application prospects as a proton exchange membrane for hydrogen fuel cells. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 (a) is the SPP-BAF prepared in Example 1. 1 HNMR, (b) 19 F NMR spectrum.

[0023] Figure 2 The Fourier transform infrared spectrum of the SPP-BAF membrane prepared in Example 1 is shown.

[0024] Figure 3 The conductivity is that of the SPP-BAF membrane prepared in Example 1.

[0025] Figure 4The water absorption rate is the value of the SPP-BAF membrane prepared in Example 1.

[0026] Figure 5 (a) is the SPP-PAF prepared in Example 4. 1 H NMR, (b) 19 F NMR spectrum.

[0027] Figure 6 The Fourier transform infrared spectrum of the SPP-PAF film prepared in Example 4 is shown.

[0028] Figure 7 The conductivity is that of the SPP-PAF membrane prepared in Example 4.

[0029] Figure 8 The water absorption rate is the value of the SPP-PAF membrane prepared in Example 4. Detailed Implementation

[0030] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] The monomer I used in Examples 1, 3, 4, 7, and 10 is:

[0032] The monomer I used in Examples 2, 5, and 9 is: The monomer I used in Examples 6 and 8 is:

[0033] Example 1

[0034] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0035] In a 100 mL three-necked flask, monomer I (0.4899 g), 2,2-bis(4-chlorophenyl)hexafluoropropane (0.0653 g), K₂CO₃ (0.0498 g), 2,2'-bipyridine (0.3115 g), and DMSO (4.7 mL) were added. The mixture was heated in a temperature-controlled oil bath at 160 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)₂ (0.5225 g) was added to the mixture. After reacting at 80 °C for 3 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer (SPP-BAF) was obtained by drying overnight in a vacuum oven at 80 °C.

[0036] Preparation of proton exchange membrane: The SPP-BAF obtained in Example 1 was dissolved in DMSO to prepare a 3% mass fraction solution. After filtration, the solution was cast onto a glass plate, heated to remove the membrane, immersed in hydrochloric acid aqueous solution, washed with deionized water until neutral, and dried to obtain the proton exchange membrane.

[0037] Figure 1 The NMR spectrum of the SPP-BAF prepared in Example 1 is shown below. Figure 1 (a): 1 ¹H NMR: The peak in the aromatic region of 6.0-8.0 ppm is due to the H proton on the benzo-polyphenyl group. Figure 1 (b): 19 The F NMR spectrum showed a set of peaks at -63 ppm, corresponding to the F peaks in -CF3, and the polymer structure was further confirmed by infrared spectroscopy. Figure 2 Several characteristic absorption peaks were observed in the FT-IR spectrum (1120, 1004, 634 cm⁻¹). -1 The absorption peak for sulfonic acid groups is 705 cm⁻¹. -1 The absorption peak generated by -CF3 proves the successful preparation of the SPP-BAF series membranes.

[0038] The molecular weight of SPP-BAF prepared in Example 1 was measured by GPC (Table 1). n =59.8kDa, M w =206.3kDa, M w / M n =3.45.

[0039] Table 1

[0040] Membrane <![CDATA[M n (kDa)]]> <![CDATA[M w (kDa)]]> <![CDATA[M w / M n ]]> SPP-BAF 59.8 206.3 3.45

[0041] Proton conductivity testing: The in-plane proton conductivity of the proton exchange membrane was determined using AC impedance spectroscopy and compared with that of the Nafion 211 membrane. Figure 3As shown in the figure, the molecular weight of the SPP-BAF membrane is higher than that of the Nafion 211 membrane within the test range, and the proton conductivity of SPP-BAF at 80℃ and 100% RH is 460.82 mS / cm. -1 .

[0042] Water absorption rate test: The water absorption rate of the SPP-BAF membrane prepared in Example 1 was tested at different temperatures under fully hydrated conditions. The SPP-BAF membrane was tested within different temperature ranges. Figure 4 The water absorption rate of the SPP-BAF membrane is higher than that of the Nafion membrane, and the water absorption rate of the SPP-BAF membrane at 80℃ is 4 times that of the Nafion membrane.

[0043] The SPP-BAF prepared in Example 1 was applied to a fuel cell. Under conditions of 80°C, 100% RH, and H2 / Air, the maximum power density of the fuel cell was 0.535 W / cm². -2 .

[0044] Example 2

[0045] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0046] In a 100 mL three-necked flask, monomer I (0.6457 g), 4,4'-dibromo-1,1'-biphenyl (0.1357 g), K₂CO₃ (0.0622 g), 2,2'-bipyridine (0.5312 g), and DMSO (8.0 mL) were added. The mixture was heated in a temperature-controlled oil bath at 160 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)₂ (1.2728 g) was added to the mixture. After reacting at 80 °C for 4 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0047] Example 3

[0048] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0049] In a 100 mL three-necked flask, monomer I (0.6124 g), 4,4”-dichloro-3,3”-bis(trifluoromethyl)-1,1’:4’,1”-terphenyl (0.0789 g), KOH (0.0252 g), 2,2’-bipyridine (0.3649 g), and DMSO (7.6 mL) were added. The mixture was heated in a temperature-controlled oil bath at 150 °C for 3 hours under N2 using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)2 (0.6121 g) was added to the mixture. After reacting at 80 °C for 4 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer (SPP-TPF) was obtained by drying overnight in a vacuum oven at 80 °C.

[0050] Preparation of proton exchange membrane: The SPP-TPF obtained in Example 3 was dissolved in DMAc to prepare a 3% mass fraction solution. After filtration, the solution was cast onto a glass plate, heated to remove the membrane, immersed in hydrochloric acid aqueous solution, washed with deionized water until neutral, and dried to obtain the proton exchange membrane.

[0051] NMR analysis of the SPP-TPF obtained in Example 3 1 ¹H NMR: The peak in the aromatic region of 6.0-8.0 ppm is due to the H proton on the benzo-polyphenyl group. 19 The F NMR spectrum shows a set of peaks at -60.60 ppm, corresponding to F in -CF3.

[0052] Proton conductivity test: The in-plane proton conductivity of the proton exchange membrane was determined using the AC impedance method. At 80℃ and 100% RH, the proton conductivity of SPP-TPF was 157.45 mS / cm. -1 .

[0053] The SPP-TPF prepared in Example 3 was applied to a fuel cell, and the maximum power density of the fuel cell at 80°C and 100% RH was 0.554 W / cm². -2 .

[0054] Example 4

[0055] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0056] In a 100 mL three-necked flask, monomer I (0.6124 g), 3,3'-(perfluorohexane-1,6-diyl)bis(chlorobenzene) (0.0764 g), Na₂CO₃ (0.0477 g), 2,2'-bipyridine (0.3418 g), and DMAc (4.2 mL) were added. The mixture was heated in a temperature-controlled oil bath at 170 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(OAc)₂ (0.3440 g) was added to the mixture. After reacting at 80 °C for 3.5 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer (SPP-PAF) was obtained by drying overnight in a vacuum oven at 80 °C.

[0057] Preparation of proton exchange membrane: The SPP-PAF obtained in Example 4 was dissolved in DMSO to prepare a 3% mass fraction solution. After filtration, the solution was cast onto a glass plate, heated to remove the membrane, immersed in hydrochloric acid aqueous solution, washed with deionized water until neutral, and dried to obtain the proton exchange membrane.

[0058] Figure 5 The NMR spectrum of the SPP-PAF obtained in Example 4 is shown below. Figure 5 (a): 1 ¹H NMR: The peak in the aromatic region at 6.0-8.2 pp m is due to the H proton on the benzo-polyphenyl group. Figure 5 (b): 19 The F NMR spectrum showed three sets of peaks at -109, -121, and -121.9 ppm, corresponding to the F atoms of the three -CF2 groups. Infrared spectroscopy was used to further confirm the polymer structure. Figure 6 Several characteristic absorption peaks were observed in the FT-IR spectrum (1140, 996, 637 cm⁻¹). -1 The absorption peak for sulfonic acid groups is 751 cm⁻¹. -1 The absorption peak generated by -CF2 proves the successful preparation of the SPP-PAF series membranes.

[0059] The molecular weight of the SPP-PAF prepared in Example 4 was measured by GPC (Table 2). n =37.1kDa, M w =150.0kDa, M w / M n =4.04.

[0060] Table 2

[0061] Membrane <![CDATA[M n (kDa)]]> <![CDATA[M w (kDa)]]> <![CDATA[M w / M n ]]> SPP-PAF 37.1 150.0 4.04

[0062] Proton conductivity testing: The in-plane proton conductivity of the proton exchange membrane was determined using AC impedance spectroscopy and compared with that of the Nafion 211 membrane. Figure 7 As shown, the conductivity of SPP-PAF is comparable to that of Nafion 211 membrane, and at 80°C and 100% RH, the proton conductivity of SPP-PAF is 145.23 mS / cm. -1 .

[0063] Water absorption rate test: The water absorption rate of the SPP-PAF membrane prepared in Example 4 was tested at different temperatures under fully hydrated conditions. The SPP-PAF membrane was tested at different temperature ranges. Figure 8 The water absorption rate of SP P-PAF membrane is higher than that of Nafion membrane, and the water absorption rate of SP P-PAF membrane is twice that of Nafion membrane at 80℃.

[0064] The SPP-PAF prepared in Example 4 was applied to a fuel cell, and at 80°C and 100% RH, the maximum power density of the fuel cell was 0.515 W / cm². -2 .

[0065] Example 5

[0066] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0067] Monomer I (0.4899 g), NaOH (0.0137 g), 2,2'-bipyridine (0.1866 g), and NMP (3 mL) were added to a 100 mL three-necked flask. The mixture was heated in a temperature-controlled oil bath at 170 °C for 2.5 hours under N2 using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(OAc)2 (0.3130 g) was added to the mixture. After reacting at 80 °C for 3 hours, the mixture was poured into a large amount of excess 4 M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer (SPPs) was obtained by drying in a vacuum oven at 80 °C overnight.

[0068] Preparation of proton exchange membrane: The SPPs obtained in Example 5 were dissolved in DMAc to prepare a 3% mass fraction solution. After filtration, the solution was cast onto a glass plate, heated to remove the membrane, immersed in hydrochloric acid aqueous solution, washed with deionized water until neutral, and dried to obtain the proton exchange membrane.

[0069] NMR analysis of the SPPs obtained in Example 5 1 ¹H NMR: The peak in the aromatic region of 6.0-8.0 ppm is due to the H proton on the benzo-polyphenyl group.

[0070] Proton conductivity test: The in-plane proton conductivity of the proton exchange membrane was determined by AC impedance spectroscopy. At 80℃ and 100% RH, the proton conductivity of SPPs was 151 mS / cm. -1 .

[0071] When the SPPs prepared in Example 5 were applied to a fuel cell, the maximum power density of the fuel cell was 0.526 W / cm² at 80°C, 100% RH, and H₂ / Air conditions. -2 .

[0072] Example 6

[0073] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0074] In a 100 mL three-necked flask, monomer I (0.6810 g), 3,3'-(perfluorobutane-1,4-diyl)bis(iodobenzene) (0.1138 g), K₂CO₃ (0.0622 g), 2,2'-bipyridine (0.3691 g), and DMSO (5.6 mL) were added. The mixture was heated in a temperature-controlled oil bath at 160 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)₂ (2.6534 g) was added to the mixture. After reacting at 80 °C for 4 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0075] Example 7

[0076] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0077] In a 100 mL three-necked flask, monomer I (0.9798 g), 1,6-bis(3-chlorophenyl)hexane (0.1374 g), Na₂CO₃ (0.0763 g), 2,2'-bipyridine (0.3271 g), and DMAc (10.4 mL) were added. The mixture was heated in a temperature-controlled oil bath at 170 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(OAc)₂ (4.9382 g) was added to the mixture. After reacting at 80 °C for 3.5 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0078] Example 8

[0079] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0080] In a 100 mL three-necked flask, monomer I (0.2043 g), 3,3'-(perfluorobutane-1,4-diyl)bis(iodobenzene) (0.6650 g), K₂CO₃ (0.3110 g), 2,2'-bipyridine (11.9443 g), and DMSO (12.7 mL) were added. The mixture was heated in a temperature-controlled oil bath at 160 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)₂ (6.0103 g) was added to the mixture. After reacting at 80 °C for 4 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0081] Example 9

[0082] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0083] In a 100 mL three-necked flask, monomer I (0.6457 g), 4,4'-dibromo-1,1'-biphenyl (0.1357 g), K₂CO₃ (0.0622 g), 2,2'-bipyridine (0.5312 g), and DMSO (8.0 mL) were added. The mixture was heated in a temperature-controlled oil bath at 160 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(COD)₂ (1.2728 g) was added to the mixture. After reacting at 80 °C for 4 hours, the mixture was poured into a large amount of excess 6M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0084] Example 10

[0085] A method for preparing a random copolymer sulfonated phenyl ionomer material for fuel cells includes the following steps:

[0086] In a 100 mL three-necked flask, monomer I (0.9798 g), 1,6-bis(3-chlorophenyl)hexane (0.003 g), Na₂CO₃ (0.0763 g), 2,2'-bipyridine (0.3271 g), and DMAc (1 mL) were added. The mixture was heated in a temperature-controlled oil bath at 170 °C for 2 hours under N₂ using a Dean Stark water separator. After azeotropic dehydration, the mixture was cooled to 80 °C. Ni(OAc)₂ (4.9382 g) was added to the mixture. After reacting at 100 °C for 1 hour, the mixture was poured into a large amount of excess 4M HCl to precipitate the product. The crude product was washed several times with concentrated HCl and deionized water. The copolymer was obtained by drying overnight in a vacuum oven at 80 °C.

[0087] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A random copolymer sulfonated phenyl ionomer material for fuel cells, characterized in that, The structural formula is: Where R is or R1, R2, R3, R4, R5, and R6 are independently selected from H, F, and -(CF2), respectively. x At least one of CF3, -CF3 and phenyl, n1 is an integer from 0 to 10 and n1 is not 0; n2 is an integer from 0 to 12 and x is an integer from 0 to 15; m:n = 1:(0-99), and n is not 0.

2. The method for preparing the random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 1, characterized in that, The process includes the following steps: mixing monomer I, monomer II, catalyst, alkaline regulator, and solvent to obtain a reaction solution and performing a coupling reaction; after the reaction is complete, the target ionomer is obtained; the structural formulas of monomer I and monomer II are shown below: Where X is Cl, Br, or I, and R is... or R1, R2, R3, R4, R5, and R6 are independently selected from H, F, and -(CF2), respectively. x At least one of CF3, -CF3 and phenyl, where n1 is an integer from 0 to 10, n2 is an integer from 0 to 12, and x is an integer from 0 to 15.

3. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The molar ratio of monomer I to monomer II is 1:(0-99); the concentration of monomer I in the reaction solution is 0.04-0.7 mmol / mL.

4. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The solvent is any one of N,N-dimethylacetamide, dimethyl sulfoxide, or N-methylpyrrolidone.

5. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The alkaline regulator is any one or more of K2CO3, Na2CO3, LiOH, NaOH or KOH; the molar ratio of monomer I to alkaline regulator is 1:(1-20).

6. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The catalyst comprises a Ni(0) catalyst and a ligand in a molar ratio of 1:(0.2-5), wherein the Ni(0) catalyst is one of Ni(COD)2, Ni(CDT), Ni(OAc)2, NiBr2 / Zn, NiCl2 / Zn, or NiI2 / Zn; and the ligand is 2,2'-bipyridine.

7. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The total molar ratio of monomer I and monomer II to the Ni(0) catalyst is 1:(1-6).

8. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The coupling reaction is carried out at a temperature of 50-100 °C for 2-24 h.

9. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, After the reaction is complete, the reaction solution is added to the precipitant, the precipitate is filtered, and then the precipitate is washed and dried to obtain the target ionomer.

10. The method for preparing random copolymer sulfonated phenyl ionomer material for fuel cells according to claim 2, characterized in that, The precipitant is an acidic aqueous solution; the acidic aqueous solution is hydrochloric acid or sulfuric acid aqueous solution; the concentration of the acidic aqueous solution is 4-6 mol / L.

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