All-carbon-chain polyaryl polymer, ion exchange membrane and application

Abstract

According to the full-carbon-chain polyaryl polymer, the ion exchange membrane and the application, a sulfonated polymer is prepared through a coupling polymerization method for the first time, has high molecular weight, can keep good mechanical performance under the high ionization degree, has extremely low swelling in electrolyte and is not prone to aging; a rigid framework of a main chain is combined with sulfonate ions, and an obvious microphase separation structure can be formed in the membrane. In addition, when the prepared ion exchange membrane is used in a battery, conductivity and impedance tests show that the ion exchange membrane has good ion transmission capability. In the battery circulation result, the flow battery prepared from the ion exchange membrane has no obvious capacity fading after 500 cycles, and the coulombic efficiency reaches 100%, which indicates that the ion exchange membrane is suitable for the aqueous flow battery, and shows high conductivity, excellent selectivity and high energy efficiency capacity utilization rate in the battery performance; the method has strong application potential in the fields of flow cells, fuel cells, electrolyzed water, concentration cells and the like.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, and in particular relates to a full-carbon chain polyaryl polymer, an ion exchange membrane, and their applications. Background Technology

[0002] To address the overuse of fossil fuels and achieve a smooth output of electricity generated from renewable energy sources, the development of large-capacity energy storage and new energy technologies is imperative.

[0003] Ion exchange membranes are important components of some important electrochemical devices such as flow batteries, fuel cells, electrolysis devices, and concentration cells. They play a crucial role in allowing ion conduction to form a current loop while simultaneously preventing the permeation of active materials on both sides. The performance of ion exchange membranes also profoundly affects the output power, coulombic efficiency, energy efficiency, and capacity retention of these devices, making them of great research significance.

[0004] An ideal ion exchange membrane should possess high electrical conductivity, low sheet resistance, suitable ion exchange capacity, high selectivity, appropriate swelling and water absorption, high chemical stability, and good mechanical and thermal stability. Furthermore, the cost of ion exchange membranes can reach 35%-50% of the overall battery cost, significantly impacting large-scale commercial applications. Summary of the Invention

[0005] The first objective of this invention is to provide a full-carbon chain polyaryl polymer.

[0006] Therefore, the above-mentioned objective of the present invention is achieved through the following technical solution:

[0007] A full-carbon-chain polyaryl polymer, the chemical structural formula of which is shown below:

[0008]

[0009] In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl;

[0010] R 1 R 2 R 3 R 4 Each is independently selected from the following group: with or without chemical bonds (no chemical bonds, i.e., R). 1 or R 2 or R 3 or R 4(The structures connected are not linked by any chemical bonds), substituted or unsubstituted C1-C10 alkyl, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl;

[0011] R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid;

[0012] r1, r2, r3, and r4 are each independently selected from 0, 1, 2, 3, 4, 5, and 6;

[0013] Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups:

[0014]

[0015] In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0016] R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl;

[0017] R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K+ Mg 2+ Al 3+ Ca 2+ Q is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups.

[0018] m1, m2, m3, and m4 are each independently selected from 0, 1, 2, 3, 4, 5, and 6;

[0019] X is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ;

[0020] Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen.

[0021] While adopting the above technical solutions, the present invention may also adopt or combine the following technical solutions:

[0022] As a preferred technical solution of the present invention: Preferred structures are those substituted or unsubstituted from the following group:

[0023]

[0024] As a preferred embodiment of the present invention, the monomers of the full-carbon chain polyaryl polymer are selected from the following group:

[0025]

[0026] In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl;

[0027] R 1 R 2 R 3 R 4 Each is independently selected from the following group: C1-C10 alkyl with or without chemical bonds, substituted or unsubstituted, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl;

[0028] R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid;

[0029] p, r1, r2, r3, r4, m1, m2, m3, m4 are each independently selected from 0, 1, 2, 3, 4, 5, 6;

[0030] Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups:

[0031]

[0032] In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0033] R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl;

[0034] R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K + Mg 2+ Al 3+ Ca 2+ Q from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups.

[0035] X is selected from the following group: F - Cl - ,Br - I - OH - OAc -OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ;

[0036] R 15 R 16 R 17 R 18 R 19 Each is independently selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl groups, C1-C10 heteroalkyl groups containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 heterocycloalkyl groups, substituted or unsubstituted C4-C12 bridged cycloalkyl groups, substituted or unsubstituted C5-C12 spirocycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, and substituted or unsubstituted C6-C10 heteroaryl groups.

[0037] Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen.

[0038] As a preferred embodiment of the present invention: monomers s-1 and s-2 are preferably substituted or unsubstituted from the following group:

[0039]

[0040]

[0041] As a preferred embodiment of the present invention: monomers s-3 and s-4 are preferably substituted or unsubstituted from the following group:

[0042]

[0043] As a preferred embodiment of the present invention: monomers s-5 and s-6 are preferably substituted or unsubstituted from the following group:

[0044]

[0045]

[0046] As a preferred embodiment of the present invention, the full-carbon chain polyaryl polymer preferably has a structure substituted or unsubstituted from the following group:

[0047]

[0048]

[0049] The second objective of this invention is to provide a method for preparing a full-carbon chain polyaryl polymer.

[0050] Therefore, the above-mentioned objective of the present invention is achieved through the following technical solution:

[0051] A method for preparing a full-carbon chain polyaryl polymer includes the following steps:

[0052] S1, Palladium-catalyzed coupling polymerization: Copolymerization of at least one of the compounds shown in formulas s-1 and s-2 with at least one of the compounds shown in formulas s-3, s-4, s-5, or s-6 yields an unsulfonated polymer.

[0053]

[0054] In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl;

[0055] R 1 R 2 R 3 R 4 Each is independently selected from the following group: C1-C10 alkyl with or without chemical bonds, substituted or unsubstituted, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl;

[0056] R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid;

[0057] p, r1, r2, r3, r4, m1, m2, m3, m4 are each independently selected from 0, 1, 2, 3, 4, 5, 6;

[0058] Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups:

[0059]

[0060] In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0061] R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl;

[0062] R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K + Mg 2+ Al 3+ Ca 2+ Q from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2- ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups.

[0063] X is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ;

[0064] R 15 R 16 R 17 R 18 R 19 Each is independently selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl groups, C1-C10 heteroalkyl groups containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 heterocycloalkyl groups, substituted or unsubstituted C4-C12 bridged cycloalkyl groups, substituted or unsubstituted C5-C12 spirocycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, and substituted or unsubstituted C6-C10 heteroaryl groups.

[0065] Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen.

[0066] S2. The polymerization system obtained in step S1 is sulfonated. The sulfonating agent is sulfuric acid, fuming sulfuric acid, or chlorosulfonic acid to obtain a sulfonated polymer. This polymer solvent is then dissolved and used for film deposition in a polar organic solvent.

[0067] S3. The polymer membrane obtained in step S2 is subjected to ion exchange to obtain a full carbon chain polyaryl polymer; the chemical structural formula of the full carbon chain polyaryl polymer is shown above.

[0068] The third objective of this invention is to provide the application of full-carbon chain polyaryl polymers in the preparation of ion exchange membranes.

[0069] Therefore, the above-mentioned objective of the present invention is achieved through the following technical solution:

[0070] The application of full-carbon chain polyaryl polymers in the preparation of ion exchange membranes, as described above, includes the following steps:

[0071] S1. Lay the full-carbon chain polyaryl polymer as described above on the plate;

[0072] S2. Drying step S1 involves laying a plate with a full carbon chain polyaryl polymer to obtain an ion exchange membrane.

[0073] A fourth objective of this invention is to provide an ion exchange membrane prepared using the applications described above.

[0074] Another objective of this invention is to provide the application of the ion exchange membrane described above in flow batteries, fuel cells, electrolysis devices, or concentration cells.

[0075] The battery system is selected from the following group: neutral, acidic, and alkaline battery systems.

[0076] The electrolyte for the battery system is selected from: aqueous solutions of sodium chloride or potassium chloride, aqueous solutions of sodium hydroxide or potassium hydroxide, sulfuric acid solution, etc.

[0077] Throughout the text, alkyl groups include straight-chain or branched alkyl groups. "C1-C10 alkyl" refers to straight-chain or branched alkyl groups having 1 to 10 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl, etc.; preferably ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl.

[0078] "C1-C10" refers to having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, "C3-C6" refers to having 3, 4, 5 or 6 carbon atoms, and so on.

[0079] "3- to 10-membered heterocyclic rings" refer to heterocyclic groups with 3 to 10 carbon atoms or heteroatoms (selected from N, O, and S). They can be saturated or partially unsaturated cyclic groups, such as tetrahydropyrrole, hexahydropyridyl, or similar groups.

[0080] "Aryl" or "aromatic ring" refers to a hydrocarbon moiety containing one or more aromatic rings, such as phenyl (Ph), naphthyl, pyrene, fluorenyl, anthracene, and phenanthrene.

[0081] "Heteroaryl" refers to a moiety containing one or more aromatic rings having at least one heteroatom (selected from N, O, S), such as furanyl, pyrroleyl, thiopheneyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, and indoleyl.

[0082] Halogens are F, Cl, Br or I.

[0083] Electrochemical devices: As one of the core components of flow batteries, ion exchange membranes play a crucial role in aqueous flow batteries by selectively allowing balance ions to pass through, forming a complete current loop, and preventing the penetration of active materials. Their cost accounts for more than 35% of the total battery cost. However, currently available commercial ion exchange membranes (Nafion series) suffer from problems such as severe active material permeation and low ionic conductivity, making it impossible to guarantee the long-term, efficient operation of these devices.

[0084] This invention provides a full-carbon-chain polyaryl polymer, an ion exchange membrane, and its applications. This invention is the first to prepare a sulfonated polymer via coupling polymerization, which has a high molecular weight, maintains good mechanical properties under high ionization levels, exhibits extremely low swelling in electrolytes, and is not prone to aging. The rigid backbone of the main chain combines with sulfonate ions to form a distinct microphase separation structure within the membrane. Furthermore, the ion exchange membrane prepared by this invention is used in batteries, and conductivity and impedance tests demonstrate its excellent ion transport capabilities. In battery cycling results, the flow battery prepared with the ion exchange membrane of this invention showed no significant capacity decay after 500 cycles, achieving a coulombic efficiency of 100%. This indicates that this type of ion exchange membrane is suitable for aqueous flow batteries, exhibiting high conductivity, excellent selectivity, and high energy efficiency and capacity utilization, significantly outperforming currently commercially available membranes such as the Nafion series and E620(K). Simultaneously, due to its high conductivity, low swelling, and low active material permeability, it has strong application potential in flow batteries, fuel cells, water electrolysis, concentration cells, and other fields. Attached Figure Description

[0085] Figure 1 The graph shows the conductivity test results of ion exchange membrane 3.

[0086] Figure 2 This is the potentiostatic impedance spectrum of ion-exchange membrane 3.

[0087] Figure 3 The results are the performance test results of the flow battery with ion exchange membrane 3.

[0088] Figure 4 The results show the long-term cycle stability test results of the flow battery with ion membrane 3.

[0089] Figure 5 The graph shows the conductivity test results for ion exchange membrane 1.

[0090] Figure 6 This is the potentiostatic impedance spectrum of ion-exchange membrane 1.

[0091] Figure 7 The graph shows the conductivity test results of ion exchange membrane 2.

[0092] Figure 8 This is the potentiostatic impedance spectrum of ion-exchange membrane 2.

[0093] Figure 9 The graph shows the conductivity test results for ion exchange membrane 4.

[0094] Figure 10 This is the potentiostatic impedance spectrum of ion-exchange membrane 4. Detailed Implementation

[0095] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

[0096] Example 1: Synthesis of Ionic Polymer 1 and Lamination of Thin Film 1

[0097] In a glove box, dibromo monomer Br-1 (203 mg, 0.5 mmol), borate ester monomer B-1 (1 eq, 320 mg), catalyst (0.025 eq, 0.0064 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 2 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 330 mg of product, with a yield of approximately 100%.

[0098]

[0099] In a glove box, dibromo monomer Br-1 (203 mg, 0.5 mmol), borate ester monomer B-1 (1 eq, 320 mg), catalyst (0.025 eq, 0.0064 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 2 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 330 mg of product, with a yield of approximately 100%.

[0100] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 50 °C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50 °C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78 °C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 1 with potassium ions as the counter ion.

[0101] Dynamic thermomechanical analysis showed that the Young's modulus of film 1 reached 0.2 GPa and the maximum tensile strength reached 12.6 MPa. Atomic force microscopy and small-angle X-ray scattering confirmed that film 1 has a distinct microphase separation structure. Conductivity tests and flow cell resistance tests confirmed that film 1 has good electrochemical performance.

[0102] Example 2: Synthesis of Ionic Polymer 2 and Lamination of Thin Film 2

[0103] In a glove box, dibromo monomer Br-2 (490 mg, 1 mmol), borate ester monomer B-1 (1 eq, 642 mg), catalyst (0.025 eq, 0.0128 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture underwent three cycles of liquid nitrogen freezing for deoxygenation. The system was then heated to 100 °C and reacted for 2 hours for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was dried under vacuum to obtain approximately 750 mg of product, with a yield of approximately 100%.

[0104] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 2 with potassium ions as the counter ion.

[0105]

[0106] Dynamic thermomechanical analysis showed that the Young's modulus of film 2 reached 0.48 GPa and the maximum tensile strength reached 32.1 MPa. Atomic force microscopy and small-angle X-ray scattering confirmed that film 2 has a distinct microphase separation structure. Conductivity tests and flow cell resistance tests confirmed that film 2 has good electrochemical performance.

[0107] Example 3 Synthesis of Ionic Polymer 3 and Lamination of Thin Film 3

[0108]

[0109] In a glove box, dibromo monomer Br-3 (660 mg, 1 mmol), borate ester monomer B-1 (1 eq, 642 mg), catalyst (0.025 eq, 0.0128 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture underwent three cycles of liquid nitrogen freezing for deoxygenation. The system was then heated to 100 °C and reacted for 2 hours for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was dried under vacuum to obtain approximately 900 mg of polymer, with a yield of approximately 100%.

[0110] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 3 with potassium ions as the counter ion.

[0111] Dynamic thermomechanical analysis showed that the Young's modulus of film 3 reached 0.49 GPa and the maximum tensile strength reached 35.4 MPa. Atomic force microscopy and small-angle X-ray scattering confirmed that film 3 has a distinct microphase separation structure. Conductivity tests and flow cell resistance tests confirmed that film 3 has good electrochemical performance.

[0112] Example 4: Synthesis of Ionomer 4 and Preparation of Thin Film 4

[0113] In a glove box, dibromo monomer Br-4 (386 mg, 0.5 mmol), borate ester monomer B-1 (1 eq, 320 mg), catalyst (0.025 eq, 0.0064 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 2 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain 1000 mg of polymer, with a yield of approximately 100%.

[0114]

[0115] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a brown casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow, transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0116] Dynamic thermomechanical analysis showed that the Young's modulus and maximum tensile strength of film 4 reached 0.1 GPa and 12.5 MPa, respectively. Atomic force microscopy and small-angle X-ray scattering confirmed that film 4 has a distinct microphase separation structure. Conductivity tests and flow cell resistance tests confirmed that film 4 has good electrochemical performance.

[0117] Example 5: Synthesis of Ionic Polymer 5 and Lamination of Thin Film 5

[0118]

[0119] In a glove box, dibromo monomer Br-2 (492 mg, 1 mmol), borate ester monomer B-2 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 450 mg of polymer, with a yield of approximately 100%.

[0120] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0121] Example 6: Synthesis of Ionic Polymer 6 and Lamination of Thin Film 6

[0122]

[0123] In a glove box, dibromo monomer Br-3 (660 mg, 1 mmol), borate ester monomer B-2 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 580 mg of polymer, with a yield of approximately 100%.

[0124] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0125] Example 7 Synthesis of Ionic Polymer 7 and Lamination of Thin Film 7

[0126] In a glove box, dibromo monomer Br-4 (772 mg, mmol), borate ester monomer B-2 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was dried under vacuum to obtain approximately 690 mg of polymer, with a yield of approximately 100%.

[0127]

[0128] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0129] Example 8: Synthesis of Ionomer 8 and Lamination of Thin Film 8

[0130] In a glove box, dibromo monomer Br-2 (492 mg, mmol), borate ester monomer B-3 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 450 mg of polymer, with a yield of approximately 100%.

[0131]

[0132] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0133] Example 9: Synthesis of Ionic Polymer 9 and Lamination of Thin Film 9

[0134]

[0135] In a glove box, dibromo monomer Br-3 (492 mg, mmol), borate ester monomer B-3 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 580 mg of polymer, with a yield of approximately 100%.

[0136] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane with potassium ions as the counter ion.

[0137] Example 10: Synthesis of Ionomer 10 and Lamination of Thin Film 10

[0138]

[0139] In a glove box, dibromo monomer Br-4 (772 mg, mmol), borate ester monomer B-3 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was dried under vacuum to obtain approximately 690 mg of polymer, with a yield of approximately 100%.

[0140] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 10 with potassium ions as the counter ion.

[0141] Example 11 Synthesis of Ionomer 11 and Thin Film 11 Lamination

[0142]

[0143] In a glove box, dibromo monomer Br-5 (312 mg, 1 mmol), borate ester monomer B-2 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 100 mg of polymer, with a yield of approximately 43%.

[0144] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 11 with potassium ions as the counter ion.

[0145] Example 12 Synthesis of Ionomer 12 and Thin Film 12 Lamination

[0146] In a glove box, dibromo monomer Br-5 (312 mg, 1 mmol), borate ester monomer B-3 (1 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 90 mg of polymer, with a yield of approximately 39%.

[0147]

[0148] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 12 with potassium ions as the counter ion.

[0149] Example 13 Synthesis of Ionomer 13 and Thin Film 13 Lamination

[0150] In a glove box, dibromo monomer Br-2 (660 mg, 1 mmol), borate ester monomer B-1 (0.5 eq, 330 mg), borate ester monomer B-2 (0.5 eq, 330 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 680 mg of polymer, with a yield of approximately 100%.

[0151]

[0152] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 13 with potassium ions as the counter ion.

[0153] Example 14 Synthesis of Ionomer 14 and Fabrication of Thin Film 14

[0154]

[0155] In a glove box, dibromo monomer Br-3 (492 mg, mmol), borate ester monomer B-3 (0.5 eq, 330 mg), borate ester monomer B-1 (0.5 eq, 642 mg), catalyst (0.05 eq, 0.046 g), ligand (0.1 eq, 0.04 g), and solvent were placed in a Schlenk flask. Outside the glove box, 2 M K₂CO₃ solution was added, and the mixture was subjected to three liquid nitrogen freezing treatments for deoxygenation. The system was then heated to 100 °C and reacted for 24 h for coupling polymerization. After cooling, the polymerization system was diluted with dichloromethane, and the polymer was precipitated in methanol. The polymer was repeatedly soaked and washed with deionized water and ethanol to remove inorganic salts and water. This dissolution, precipitation, and washing process was repeated three times. The resulting grayish-white polymer was vacuum dried to obtain approximately 560 mg of polymer, with a yield of approximately 100%.

[0156] The dried, grayish-white polymer was dissolved in dichloromethane under high temperature and pressure in a sealed tube. The solution was filtered to remove insoluble matter, and then placed in a 250 mL round-bottom flask. A dichloromethane solution of chlorosulfonic acid was added dropwise at 0°C, and sulfonation was carried out for 5 min. After the reaction, excess acid was washed away with deionized water. The solution was then sonicated, stirred, filtered, and vacuum dried at 50°C to obtain a yellow polymer. An appropriate amount of the polymer was weighed and dissolved in 15 mL of DMSO to obtain a yellow casting solution. This casting solution was poured onto a horizontal glass plate (9 cm × 9 cm), allowing the liquid to spread naturally. After drying at 78°C for 24 hours, a yellow transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M potassium hydroxide solution to obtain an ion exchange membrane 14 with potassium ions as the counter ion.

[0157] Electrochemical performance testing of membranes

[0158] Test 1: Conductivity Test Using the Four-Electrode Method

[0159] The ionic conductivity of the membrane (1 cm × 4 cm) was measured using the four-electrode method. Figure 1 , 5 As shown in Figures 7 and 9, the membranes all exhibit good electrical conductivity. At 30°C, the conductivity of the membranes is in the range of 25-40 mS / cm, and at 70°C, the potassium ion conductivity is in the range of 60-80 mS / cm, which is at a leading level in the field.

[0160] Test 2: Membrane Impedance Test

[0161] Impedance testing of the membrane (3cm×3cm×25μm) was performed using a flow battery assembled in the laboratory and an Autolab electrochemical workstation. During the battery test, the positive electrode was 5 mL of 2M potassium chloride solution containing 0.4M potassium ferrocyanide, and the negative electrode was 5 mL of 1.4M potassium hydroxide + 0.6M KCl solution containing 0.4M 1,8-PFP.

[0162] like Figure 2 , 6 As shown in Figures 8 and 10, taking ion exchange membrane 3 (membrane thickness 25 μm) as an example, its impedance test result is 0.30 Ω·cm. 2 It is superior to Nafion series membranes (0.70 Ω·cm) under the same conditions. 2 ) and E620(K) film (1.10Ω·cm) 2 ).

[0163] Test 3: Flow Battery Performance Test

[0164] The battery performance of the membrane (3cm×3cm×25μm) was tested using a self-assembled flow battery and an Autolab electrochemical workstation. An ion exchange membrane 3 (3cm×3cm×24μm, impedance 0.30Ω·cm) was used. 2 The battery was assembled using carbon cloth as the electrode material. During battery testing, the positive electrode was 5 mL of a 2 M potassium chloride solution containing 0.4 M potassium ferrocyanide, and the negative electrode was 5 mL of a 1.4 M potassium hydroxide + 0.6 M KCl solution containing 0.4 M 1,8-PFP.

[0165] like Figure 3 As shown, the cyclic voltammetry test range is 0.3-1.7V, and the maximum power of the battery at near 100% charge is 252mW / cm². 2 The magnification tests were conducted at 100 mA / cm². 2 200mA / cm 2 300mA / cm 2 400mA / cm 2 500mA / cm 2 The energy efficiencies were 74.5%, 63.8%, 52.0%, 42.0%, and 29.7% at various current densities. The coulombic efficiency consistently exceeded 99%.

[0166] Test 4: Cyclic Stability Test of Flow Batteries

[0167] Constant current charge-discharge cycle tests were performed using an electrochemical workstation. An ion exchange membrane (3 cm × 3 cm × 24 μm, impedance 1.00 Ω·cm) was used. 2 The battery was assembled using carbon cloth as the electrode material. During the constant current phase, the charge / discharge current was 2420 mA, and the current density was 500 mA / cm². 2The charging cutoff voltage is 1.7V, the discharging cutoff voltage is 0.2V, and the cycle count is 500 cycles. During battery testing, the positive electrode is 5mL of a 2M potassium chloride solution containing 0.4M potassium ferrocyanide (K2Fe(CN)4), and the negative electrode is 5mL of a 1.4M potassium hydroxide + 0.6M KCl solution containing 0.4M 1,8-PFP (chemical structure shown below). The long-cycle test results are as follows... Figure 4 As shown, during 500 constant current cycle tests, the battery showed no significant capacity decay, and the coulombic efficiency reached 100%.

[0168]

[0169] The above specific embodiments are used to explain and illustrate the present invention, and are only preferred embodiments of the present invention, not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made to the present invention within the spirit and scope of the claims shall fall within the protection scope of the present invention.

Claims

1. A full-carbon chain polyaryl polymer, characterized in that: The chemical structural formula of the full-carbon chain polyaryl polymer is shown below: In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl; R 1 R 2 R 3 R 4 Each is independently selected from the following group: C1-C10 alkyl with or without chemical bonds, substituted or unsubstituted, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl; R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid; r1, r2, r3, r4, m1, m2, m3, m4 are each independently selected from 0, 1, 2, 3, 4, 5, 6; Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups: In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl; R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K + Mg 2+ Al 3+ Ca 2+ Q from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups. m1, m2, m3, and m4 are each independently selected from 0, 1, 2, 3, 4, 5, and 6; X is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ; Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen.

2. The full-carbon chain polyaryl polymer as described in claim 1, characterized in that: Preferred structures are those substituted or unsubstituted from the following group:

3. The full-carbon chain polyaryl polymer as described in claim 1, characterized in that: The monomers of the full-carbon chain polyaryl polymer are selected from the following group: In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl; R 1 R 2 R 3 R 4 Each is independently selected from the following group: C1-C10 alkyl with or without chemical bonds, substituted or unsubstituted, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl; R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid; p, r1, r2, r3, r4, m1, m2, m3, m4 are each independently selected from 0, 1, 2, 3, 4, 5, 6; Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups: In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl; R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K + Mg 2+ Al 3+ Ca 2+ Q from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups. X is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ; R 15 R 16 R 17 R 18 R 19 Each is independently selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl groups, C1-C10 heteroalkyl groups containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 heterocycloalkyl groups, substituted or unsubstituted C4-C12 bridged cycloalkyl groups, substituted or unsubstituted C5-C12 spirocycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, and substituted or unsubstituted C6-C10 heteroaryl groups. Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen.

4. The full-carbon chain polyaryl polymer as described in claim 3, characterized in that: Monomers s-1 and s-2 are preferably derived from the following substituted or unsubstituted structures:

5. The full-carbon chain polyaryl polymer as described in claim 3, characterized in that: Monomers s-3 and s-4 are preferably derived from the following substituted or unsubstituted structures:

6. The full-carbon chain polyaryl polymer as described in claim 3, characterized in that: Monomers s-5 and s-6 are preferably derived from the following substituted or unsubstituted structures:

7. The full-carbon chain polyaryl polymer as described in claim 1, characterized in that: The full-carbon chain polyaryl polymer is preferably selected from the following substituted or unsubstituted structures:

8. A method for preparing a full-carbon chain polyaryl polymer, characterized in that: The method includes the following steps: S1, Palladium-catalyzed coupling polymerization: Copolymerization of at least one of the compounds shown in formulas s-1 and s-2 with at least one of the compounds shown in formulas s-3, s-4, s-5, or s-6 yields an unsulfonated polymer. In the above formula: Each is independently selected from the group consisting of: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and the aryl or heteroaryl is selected from the group consisting of: monocyclic aryl, fused-ring aryl, monoheterocyclic aryl, fused-heterocyclic aryl; R 1 R 2 R 3 R 4 Each is independently selected from the following group: C1-C10 alkyl with or without chemical bonds, substituted or unsubstituted, C1-C10 heteroalkyl containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C6-C10 heteroaryl; R 5 R 6 R 7 R 8 Represents one or more substituents on an aromatic ring, each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol, C1-C6 amino, carboxyl, phosphate, sulfonic acid; p, r1, r2, r3, r4, m1, m2, m3, m4 are each independently selected from 0, 1, 2, 3, 4, 5, 6; Rs 1 Rs 2 Rs 3 Rs 4 Each is independently selected from the following group: none, or the following ionic groups: In the above formula: k and j are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; R 13 R 14 Each is independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C4-C12 bridged cycloalkyl, substituted or unsubstituted C5-C12 spirocycloalkyl, substituted or unsubstituted C6-C10 aryl; R 0 Selected from the following groups: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z)3X; where Y is selected from the following group: H + NH4 + Li + Na + K + Mg 2+ Al 3+ Ca 2+ Q from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - SO4 2- SO3 2- PO4 3- HPO4 2- H2PO4 - NO2 - NO3 - CO3 2- HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - Z is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups. X is selected from the following group: F - Cl - ,Br - I - OH - OAc - OTf - OTs - HCO3 - ClO4 - ClO3 - ClO2 - ,ClO - CN - ; R 15 R 16 R 17 R 18 R 19 Each is independently selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl groups, C1-C10 heteroalkyl groups containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 heterocycloalkyl groups, substituted or unsubstituted C4-C12 bridged cycloalkyl groups, substituted or unsubstituted C5-C12 spirocycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, and substituted or unsubstituted C6-C10 heteroaryl groups. Substitution refers to the substitution of one or more hydrogen atoms in a group by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, and carboxyl; heterocycloalkyl or heteroaryl refers to a group containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen. S2. Take the polymer obtained in step S1 and perform post-functionalization, i.e., sulfonation reaction. The sulfonation reagent is sulfuric acid, fuming sulfuric acid, or chlorosulfonic acid to obtain a sulfonated polymer. Dissolve this polymer in a polar organic solvent for dissolution and film laying. S3. The polymer membrane obtained in step S2 is subjected to ion exchange to obtain a full carbon chain polyaryl polymer; the chemical structural formula of the full carbon chain polyaryl polymer is as shown in claim 1.

9. The application of the full-carbon chain polyaryl polymer as described in claim 1 in the preparation of ion exchange membranes, characterized in that: The application includes the following steps: S1. Lay the full-carbon chain polyaryl polymer as described in claim 1 flat on a plate; S2. Drying step S1 involves laying a plate with a full carbon chain polyaryl polymer to obtain an ion exchange membrane.

10. The application of the ion exchange membrane prepared according to claim 9 in flow batteries, fuel cells, electrolysis devices or concentration cells.

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