Ion exchange membrane based on branched Tegler base structure and application of ion exchange membrane

Abstract

The invention provides an ion exchange membrane based on a branched Tegler base structure and application of the ion exchange membrane, and particularly provides a compound shown as a formula (I), a formula (II) or a formula (III), and the compound can be used for preparing the ion exchange membrane with high conductivity and high ion selectivity.

Description

Technical Field

[0001] The invention belongs to the field of ion exchange membranes, and in particular relates to an ion exchange membrane based on a branched Tegler base structure and applications thereof. Background Art

[0002] Ion exchange membranes are a type of membrane material containing ionic functional groups that selectively transport ions while effectively blocking the permeation of active substances. They have important applications in separation and purification, such as desalination, acid-base recovery, and wastewater treatment, as well as clean energy applications such as flow batteries, fuel cells, and hydrogen production through water electrolysis. Performance indicators for ion exchange membranes include ionic conductivity, ion selectivity, mechanical properties, chemical stability, and swelling resistance. Ionic conductivity, representing the ability of ions to conduct through the membrane, is one of the most important indicators for evaluating membrane performance. High conductivity indicates higher ion transport efficiency, effectively reducing energy loss during the transport process. Ion exchange membranes also play an important role in blocking the permeation of active substances in the positive and negative electrodes. Reducing the permeation of active substances effectively inhibits the self-discharge process of the battery, preventing cross-contamination between the positive and negative electrode materials, thereby extending the battery life.

[0003] Aqueous flow batteries, one of the most promising large-scale energy storage technologies, can effectively address the instability of solar and wind power generation. As one of the core components, ion exchange membranes play an important role in aqueous flow batteries by selectively permeating balanced ions, forming a complete current circuit, and preventing the interpenetration of active substances. Their cost accounts for more than 35% of the total battery cost. However, the common anion exchange membranes currently available on the market face problems such as severe active substance permeation (such as DSV) and low ion conductivity (such as AMV), which cannot guarantee the long-term and efficient operation of the flow battery.

[0004] Therefore, there is an urgent need in this field to develop low-cost, high-conductivity, and high-ion-selective ion exchange membranes to solve the long-standing problem that conductivity and selectivity of ion exchange membranes cannot be achieved simultaneously. Summary of the Invention

[0005] The purpose of the present invention is to provide an ion exchange membrane with low cost, high conductivity and high ion selectivity, and in particular to an ion exchange membrane based on a branched Tegler base structure and its application.

[0006] In the first aspect of the present invention, a compound represented by the following formula (I), formula (II), or formula (III) is provided:

[0007]

[0008]

[0009] Among them, R 7Selected from the following group: N, substituted or unsubstituted C1-C10 three-arm alkyl chain, substituted or unsubstituted C6-C10 three-arm aryl, substituted or unsubstituted 6-10 membered three-arm heteroaryl, substituted or unsubstituted C3-C10 three-arm cycloalkyl, substituted or unsubstituted 3-10 membered three-arm heterocycloalkyl, substituted or unsubstituted 4-12 membered three-arm bridged cycloalkyl, substituted or unsubstituted C5-C12 three-arm spirocycloalkyl, substituted or unsubstituted C9-C18 three-arm fused ring aromatic hydrocarbon;

[0010] R 8 Each is independently selected from the following group: substituted or unsubstituted C1-C10 four-arm alkyl, substituted or unsubstituted C6-C10 four-arm aryl, substituted or unsubstituted 6-10 membered four-arm heteroaryl, substituted or unsubstituted C3-C10 four-arm cycloalkyl, substituted or unsubstituted 3-10 membered four-arm heterocycloalkyl, substituted or unsubstituted 4-12 membered four-arm bridged cycloalkyl, substituted or unsubstituted C5-C12 four-arm spirocycloalkyl, substituted or unsubstituted C9-C18 four-arm fused ring aromatic hydrocarbon; the heteroatom is selected from: N, O, S;

[0011] The

[0012] Each is independently selected from the following group: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 6-20 membered heteroaryl, wherein the aryl or heteroaryl may be a structure selected from the following group: monocyclic aryl, condensed aryl, monoheterocyclic aryl, condensed heterocyclic aryl;

[0013] The R 1 、R 2 Each independently selected from the following group: None (ie, when R 1 or R 2 There are no chemical bonds between the connected structures), 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, and R 1 、R 2 Not at the same time no or chemical bond;

[0014] The R 3 、R 4 、R 5 、R 6Each is independently selected from the following group: 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 amine, carboxyl, phosphate, sulfonic acid;

[0015] or R 1 and R 2 Together they form a cyclic structure selected from the group consisting of a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted 6-10 membered heteroaryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted 4-12 membered bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, and a substituted or unsubstituted C9-C18 fused ring aromatic hydrocarbon;

[0016] or R 1 、R 3 and R 5 , or R 2 、R 4 and R 6 Together with the ring atoms separated by it, it forms a cyclic structure selected from the group consisting of a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted 6-10 membered heteroaryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 heterocycloalkyl group, a substituted or unsubstituted 4-12 membered bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, and a substituted or unsubstituted C9-C18 fused ring aromatic hydrocarbon;

[0017] R 9 Selected from the following group: substituted or unsubstituted C1-C10 alkyl, or the following ionic groups:

[0018]

[0019] wherein k and j are each independently selected from 1, 2, 3, 4, 5, 6, 7 or 8;

[0020] R 10 、R 11 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;

[0021] R 0 Selected from the following group: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N +(Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ;Q - Select 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 following group: substituted or unsubstituted C1-C10 alkyl;

[0022] The X - Select from the following group: F - 、Cl - Br, I - OH - 、OAc - 、OTf - ,OTs - 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ;

[0023] Unless otherwise specified, the substitution refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; the heterocycloalkyl or heteroaryl refers to a group containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen.

[0024] In another preferred embodiment, the R 7 Selected from the following group: N, substituted or unsubstituted C1-C10 three-arm alkyl, substituted or unsubstituted C6-C10 three-arm aryl, substituted or unsubstituted 6-10 membered three-arm heteroaryl, substituted or unsubstituted C9-C18 three-arm condensed aromatic hydrocarbon; or a complex group composed of any two or more of the above groups;

[0025] The R 8 Selected from the following groups: substituted or unsubstituted C1-C10 four-arm alkyl, substituted or unsubstituted C6-C10 four-arm aryl, substituted or unsubstituted 6-10 membered four-arm heteroaryl, substituted or unsubstituted C9-C18 condensed ring aromatic hydrocarbon; or a complex group composed of any two or more of the above groups.

[0026] In another preferred embodiment, the

[0027] A substituted or unsubstituted structure selected from the following group:

[0028]

[0029] In another preferred embodiment, the R 1 、R 2 are each independently selected from the following group: none, a chemical bond, a substituted or unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, a substituted or unsubstituted C4-C12 bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, and R 1 、R 2 Not at the same time is none or chemical bond.

[0030] In another preferred embodiment, the R 3 、R 4 、R 5 and R 6 Each is 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, and hydroxy.

[0031] In another preferred embodiment, the R 9 Selected from the following group: substituted or unsubstituted C1-C6 alkyl, or the following ionic groups:

[0032]

[0033] k=1,2,3,4,5,6,7,8

[0034] j=1,2,3,4,5,6,7,8

[0035] R 10 、R 11 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;

[0036] R 0 Selected from the following group: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ;Q - Select 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 following group: substituted or unsubstituted C1-C10 alkyl.

[0037] In another preferred embodiment, the compound has a structure selected from the following table:

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] In another preferred embodiment, the compound is prepared by the following method:

[0044] Copolymerizing a formaldehyde source monomer, one or more of formulas A-1, A-2, A-3 and A-4 with one of the compounds of formula A1, A2 or A3 to obtain the compound of the first aspect,

[0045]

[0046]

[0047] In another preferred embodiment, the monomers A-1, A-2, A-3 and A-4 of the compound are selected from but not limited to the following structures:

[0048]

[0049] In another preferred embodiment, the monomer formula A1, formula A2 or formula A3 of the compound is selected from but not limited to the following structures:

[0050]

[0051] In another preferred embodiment, the compound has a structure selected from the following group:

[0052]

[0053] In a second aspect of the present invention, a method for preparing the compound according to the first aspect is provided, the method comprising the steps of:

[0054] (i-1) in the presence of trifluoroacetic acid, carrying out an acid-catalyzed polymerization reaction using a diamine monomer selected from one or more of Formulas A-1, A-2, A-3 and A-4, a formaldehyde source monomer, and trifluoroacetic acid;

[0055]

[0056] (i-2) After step (i-1), add A1 or A2 and continue the reaction until the system gels and solidifies to form a polymer system;

[0057]

[0058] (i-3) post-treating the polymerization system obtained in step (i-2) to perform quaternization to obtain a quaternized polymer solution;

[0059] (i-4) subjecting the quaternized polymer solution obtained in step (i-3) to ion exchange to obtain the compound of formula I or formula II described in the first aspect; or

[0060] (ii-1) acid-catalyzed polymerization of a diamine monomer selected from one or more of formulas A-1, A-2, A-3, and A-4 with a formaldehyde source monomer in the presence of trifluoroacetic acid;

[0061] (ii-2) After step (ii-1) is completed, A3 is added to form a polymerization system, and the system is coated on a plate to continue the reaction before the gel solidifies to obtain a polymer film material.

[0062]

[0063] (ii-3) taking the polymer film material obtained in step (ii-2) and post-treating it to obtain a polymer film;

[0064] (ii-4) The polymer film obtained in step (ii-3) is immersed in a methanol solution of iodomethane to react and obtain the compound of formula III described in the first aspect.

[0065] In another preferred embodiment, the formaldehyde source monomer is selected from the group consisting of formaldehyde solution, paraformaldehyde, hexamethylenetetramine, trioxane and dimethoxymethane.

[0066] In another preferred embodiment, the method comprises the steps of:

[0067] (i-1) in the presence of trifluoroacetic acid, carrying out an acid-catalyzed polymerization reaction using a diamine monomer selected from one or more of Formulas A-1, A-2, A-3, and A-4, a formaldehyde source monomer, and trifluoroacetic acid under a nitrogen atmosphere at a certain temperature with stirring;

[0068]

[0069] (i-2) After step (i-1), add A1 or A2 and continue the reaction until the system gels and solidifies to form a polymer system;

[0070]

[0071] (i-3) taking the polymerization system obtained in step (i-2) and post-treating it to obtain a white polymer;

[0072] (i-4) taking the white polymer obtained in step (i-3), stirring and reacting it in a dimethyl sulfoxide solution to perform quaternization to obtain a quaternized polymer solution;

[0073] (i-5) subjecting the quaternized polymer solution obtained in step (i-4) to ion exchange to obtain the compound of formula I or formula II described in the first aspect; or

[0074] (ii-1) providing a diamine monomer, dimethoxymethane, and trifluoroacetic acid, and stirring under a nitrogen atmosphere at a certain temperature to carry out an acid-catalyzed polymerization reaction;

[0075] (ii-2) After step (ii-1) is completed, triamine monomer A3 is added to form a polymerization system, and the system is coated on a plate to continue the reaction before the gel solidifies to obtain a polymer film material.

[0076]

[0077] (ii-3) taking the polymer film material obtained in step (ii-2) and post-treating it to obtain a polymer film;

[0078] (ii-4) The polymer film obtained in step (ii-3) is immersed in a methanol solution of iodomethane to react and obtain the compound of formula III described in the first aspect.

[0079] In another preferred embodiment, the mass ratio of the diamine monomer, dimethoxymethane and trifluoroacetic acid in step (i-1) is 1:1-2:10-20, preferably 1:1.3-1.8:11-17.

[0080] In another preferred embodiment, the temperature in step (i-1) is -5°C to 5°C.

[0081] In another preferred embodiment, the reaction time in step (i-1) is 20 h-30 h.

[0082] In another preferred embodiment, the mass ratio of the diamine monomer in step (i-1) to the triamine monomer in step (i-2) is 10-25:1, preferably 12-20:1.

[0083] In another preferred embodiment, the post-treatment in step (i-3) includes: soaking and washing the polymerization system in an ammonium hydroxide solution and deionized water to remove excess acid to obtain a white polymer.

[0084] In another preferred embodiment, step (i-3) further comprises the step of drying the obtained white polymer.

[0085] In another preferred embodiment, the ion exchange in step (i-4) specifically comprises the following steps:

[0086] (i-4-1) Spreading the quaternized polymer solution on a plate and drying it at a certain temperature to obtain an ion exchange membrane;

[0087] (i-4-2) The ion exchange membrane obtained in step (i-4-1) is subjected to ion exchange in a sodium chloride solution to obtain the compound described in the first aspect.

[0088] In a third aspect of the present invention, there is provided a use of the compound according to the first aspect for preparing an ion exchange membrane; wherein the method for preparing the ion exchange membrane comprises the steps of:

[0089] (1) providing the compound described in the first aspect and spreading it on a plate;

[0090] (2) Drying the plate of step (1) to obtain an ion exchange membrane.

[0091] In another preferred embodiment, the ion exchange membrane is used in an aqueous liquid flow battery.

[0092] In another preferred embodiment, the aqueous liquid flow battery is selected from the following group: aqueous liquid flow battery equipment under a neutral system.

[0093] In another preferred embodiment, the supporting electrolyte of the aqueous flow battery is selected from an aqueous solution of sodium chloride or potassium chloride.

[0094] In another preferred embodiment, the electrode active material of the aqueous liquid flow battery is selected from the following group: viologen, nitroxide free radical, and ferrocene active substances.

[0095] In another preferred embodiment, the positive electrode of the electrode active material of the aqueous liquid flow battery is selected from the following group:

[0096] Representative useful active material structures are selected from the following group:

[0097]

[0098] In another preferred embodiment, the negative electrode of the electrode active material of the aqueous liquid flow battery is selected from the following group:

[0099]

[0100] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features described in detail below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be listed here one by one. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 The graph shows the conductivity test results of ion membrane 1m.

[0102] Figure 2 The potentiostatic impedance spectrum of the ion membrane 1m is shown.

[0103] Figure 3The results of the flow battery performance test of ion membrane 1m are shown.

[0104] Figure 4 Shows the long-term cycle stability test results of a flow battery with 1m ion membrane.

[0105] Figure 5 This is the conductivity test result of the ion membrane 2m.

[0106] Figure 6 The potentiostatic impedance spectrum of the ion membrane 2m is shown.

[0107] Figure 7 The graph shows the conductivity test results of the ion membrane 3m;

[0108] Figure 8 The potentiostatic impedance spectrum of the ion membrane 3m is shown.

[0109] Figure 9 The graph shows the conductivity test results of the ion membrane 4m.

[0110] Figure 10 The potentiostatic impedance spectrum of the ion membrane 4m is shown.

[0111] Figure 11 The graph shows the conductivity test results of the ion membrane 5m.

[0112] Figure 12 The potentiostatic impedance spectrum of the ion membrane 5m is shown.

[0113] Figure 13 The graph shows the conductivity test results of the ion membrane 6m.

[0114] Figure 14 The potentiostatic impedance spectrum of the ion membrane 6m is shown.

[0115] Figure 15 A graph showing the conductivity test results of the ion membrane 7m.

[0116] Figure 16 The potentiostatic impedance spectrum of the ion membrane 7m is shown.

[0117] Figure 17 The graph shows the conductivity test results of the ion membrane 8m.

[0118] Figure 18 The potentiostatic impedance spectrum of the ion membrane 8m is shown.

[0119] Figure 19 The structures of the positive electrode material FcNCl and the negative electrode material BTMAP-Vi used in this article are shown. DETAILED DESCRIPTION

[0120] After extensive and intensive research and numerous experimental screenings, the inventors unexpectedly developed a compound based on a branched Tegler base structure. This compound is based on a TB polymer structure. Leveraging the rigid [3,3,1]-ring structure, the TB structure introduces branched or cross-linked structures to effectively enhance its structural stability. The resulting polymer maintains excellent mechanical properties even at high ionization levels, exhibits extremely low swelling in water, and is resistant to aging. The compound is simple to synthesize, made from readily available, inexpensive raw materials, and readily scalable for industrial production. Furthermore, ion exchange membranes prepared using this compound have been used in batteries, and conductivity and impedance testing demonstrate their excellent ion transport capabilities. Battery cycling results show that flow batteries prepared using this ion exchange membrane exhibit a capacity decay of 0.015% per cycle and a coulombic efficiency of 100%. This demonstrates the suitability of this ion exchange membrane for aqueous flow batteries, demonstrating high conductivity and excellent selectivity, significantly outperforming currently used commercial DSV and AMV membranes. Based on this foundation, the inventors developed the present invention.

[0121] Terminology

[0122] In the present invention, the alkyl group includes a linear or branched alkyl group, and the halogen group is F, Cl, Br or I.

[0123] In the present invention, the term "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.

[0124] In the present invention, the term "alkyl" refers to a saturated linear or branched hydrocarbon moiety. For example, the term "C1-C10 alkyl" refers to a straight or branched alkyl group having 1 to 10 carbon atoms, including but not limited to 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.

[0125] The term "3- to 10-membered heterocycle" refers to a heterocyclic group having 3 to 10 carbon atoms or heteroatoms (selected from N, O, and S), which may be a saturated or partially unsaturated cyclic group, such as tetrahydropyrrolyl, hexahydropyridyl, or similar groups.

[0126] In the present invention, the term "aryl" or "aromatic ring" refers to a hydrocarbon moiety containing one or more aromatic rings. Examples of aryl groups include, but are not limited to, phenyl (Ph), naphthyl, pyrenyl, fluorenyl, anthracenyl, and phenanthrenyl.

[0127] In the present invention, the term "heteroaryl" refers to a moiety containing one or more aromatic rings having at least one heteroatom, such as N, O, or S. Examples of heteroaryl groups include furyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl, among others.

[0128] In the present invention, the "compound of the present invention", "compound described in the present invention", and "compound described in the present invention" refer to the compound represented by formula (I), (II), or formula (III) prepared by the method described in the present invention.

[0129] flow batteries

[0130] Ion exchange membranes, as a core component of aqueous flow batteries, play a crucial role in selectively permeating balance ions, forming a complete current circuit, and preventing cross-contamination of active materials. Their cost accounts for over 35% of the total battery cost. However, currently, common commercially available anion exchange membranes face challenges such as severe active material cross-contamination (e.g., DSV) and low ionic conductivity (e.g., AMV), making them unable to guarantee long-term, efficient operation of flow batteries.

[0131] The present invention is based on a TB-structured polymer, utilizing the rigid [3,3,1]-ringed skeleton within the TB structure. By introducing branched or cross-linked structures, its structural stability is effectively enhanced. The resulting polymer can maintain good mechanical properties even at a high degree of ionization, exhibits extremely low swelling in water, and is not susceptible to aging. This branched TB polymer is simple to synthesize, and the raw materials are readily available and inexpensive, making it easy to scale up for industrial production. Conductivity and impedance testing demonstrate that this type of ion exchange membrane possesses excellent ion transport capabilities. Battery cycling results indicate that this type of ion exchange membrane is suitable for aqueous flow batteries, significantly outperforming the current commercial DSV and AMV membranes in terms of battery performance.

[0132] Preparation of the compounds of formula (I), (II), or (III) of the present invention

[0133] In the present invention, the preparation method of the compound comprises the steps of:

[0134] (i-1) in the presence of trifluoroacetic acid, carrying out an acid-catalyzed polymerization reaction using a diamine monomer selected from one or more of Formulas A-1, A-2, A-3 and A-4, a formaldehyde source monomer, and trifluoroacetic acid;

[0135]

[0136] (i-2) After step (i-1), add A1 or A2 and continue the reaction until the system gels and solidifies to form a polymer system;

[0137]

[0138] (i-3) post-treating the polymerization system obtained in step (i-2) to perform quaternization to obtain a quaternized polymer solution;

[0139] (i-4) subjecting the quaternized polymer solution obtained in step (i-3) to ion exchange to obtain the compound of formula I or formula II of the present invention; or

[0140] (ii-1) acid-catalyzed polymerization of a diamine monomer selected from one or more of formulas A-1, A-2, A-3, and A-4 with a formaldehyde source monomer in the presence of trifluoroacetic acid;

[0141] (ii-2) After step (ii-1) is completed, A3 is added to form a polymerization system, and the system is coated on a plate to continue the reaction before the gel solidifies to obtain a polymer film material.

[0142]

[0143] (ii-3) taking the polymer film material obtained in step (ii-2) and post-treating it to obtain a polymer film;

[0144] (ii-4) The polymer film obtained in step (ii-3) is immersed in a methanol solution of iodomethane to react and obtain the compound of formula III of the present invention.

[0145] In the present invention, the formaldehyde source monomer is selected from the following group: formaldehyde solution, paraformaldehyde, hexamethylenetetramine, trioxane and dimethoxymethane.

[0146] In another preferred embodiment, the method comprises the steps of:

[0147] (i-1) in the presence of trifluoroacetic acid, carrying out an acid-catalyzed polymerization reaction using a diamine monomer selected from one or more of Formulas A-1, A-2, A-3, and A-4, a formaldehyde source monomer, and trifluoroacetic acid under a nitrogen atmosphere at a certain temperature with stirring;

[0148]

[0149] In the present invention, the is a structure selected from the group consisting of:

[0150]

[0151] (i-2) After step (i-1), add A1 or A2 and continue the reaction until the system gels and solidifies to form a polymer system;

[0152]

[0153] (i-3) taking the polymerization system obtained in step (i-2) and post-treating it to obtain a white polymer;

[0154] (i-4) taking the white polymer obtained in step (i-3), stirring and reacting it in a dimethyl sulfoxide solution to perform quaternization to obtain a quaternized polymer solution;

[0155] (i-5) subjecting the quaternized polymer solution obtained in step (i-4) to ion exchange to obtain the compound of formula I or formula II of the present invention; or

[0156] (ii-1) providing a diamine monomer, dimethoxymethane, and trifluoroacetic acid, and stirring under a nitrogen atmosphere at a certain temperature to carry out an acid-catalyzed polymerization reaction;

[0157] (ii-2) After step (ii-1) is completed, triamine monomer is added to form a polymerization system, and the system is coated on a plate to continue the reaction before the gel solidifies to obtain a polymer film material.

[0158]

[0159] (ii-3) taking the polymer film material obtained in step (ii-2) and post-treating it to obtain a polymer film;

[0160] (ii-4) The polymer film obtained in step (ii-3) is immersed in a methanol solution of iodomethane to react and obtain the compound of formula III of the present invention.

[0161] Preferably, in step (i-1), the mass ratio of the diamine monomer, dimethoxymethane and trifluoroacetic acid is 1:1-2:10-20, more preferably 1:1.3-1.8:11-17.

[0162] Preferably, the temperature in step (i-1) is -5°C to 5°C.

[0163] Preferably, the reaction time in step (i-1) is 20 h to 30 h.

[0164] Preferably, the mass ratio of the diamine monomer in step (i-1) to the triamine monomer in step (i-2) is 10-25:1, more preferably 12-20:1.

[0165] Preferably, the post-treatment in step (i-3) comprises: soaking and washing the polymerization system in an ammonium hydroxide solution and deionized water to remove excess acid to obtain a white polymer.

[0166] Preferably, step (i-3) further comprises the step of drying the obtained white polymer.

[0167] Preferably, the ion exchange in step (i-4) specifically comprises the following steps:

[0168] (i-4-1) Spreading the quaternized polymer solution on a plate and drying it at a certain temperature to obtain an ion exchange membrane;

[0169] (i-4-2) The ion exchange membrane obtained in step (i-4-1) is subjected to ion exchange in a sodium chloride solution to obtain the compound of the present invention.

[0170] Compared with the prior art, the present invention has the following beneficial effects:

[0171] 1. The compounds of the present invention (ionic polymers) are polymers based on the TB structure. The rigid skeleton of the [3,3,1] ring in the TB structure is utilized to effectively enhance its structural stability by introducing branched or cross-linked structures. The resulting polymers can maintain good mechanical properties at a high degree of ionization, have extremely low swelling in water, and are not easily aged.

[0172] 2. The compound (ionic polymer) of the present invention is simple to synthesize, the raw materials are cheap and readily available, and it is easy to expand the scale of industrial production.

[0173] 3. The ion exchange membrane prepared from the compound (ionic polymer) of the present invention has good ion transmission capacity. The capacity decay of the prepared liquid flow battery is 0.015% per cycle, and the coulombic efficiency reaches 100%. It is suitable for aqueous liquid flow batteries and exhibits high conductivity and excellent selectivity in battery performance. Its battery performance is significantly better than the current commercial membranes DSV and AMV membranes.

[0174] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples, for which specific conditions are not specified, are generally based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are by weight.

[0175] Example 1 Synthesis of Ionic Polymer 1 and Fabrication of Thin Film 1m

[0176]

[0177] Acid-catalyzed polymerization of diamine monomer 9 (226 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.42 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. After polymerization, triamine monomer 10 (0.05 eq, 14.5 mg) was added and allowed to react until the system gelled and solidified to obtain a polymerization system. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum dried to yield 264 mg of polymer, with a theoretical yield of 281 mg and a yield of 94%.

[0178] The dried white polymer was quaternized by vigorously stirring it in 10 mL of DMSO (dimethyl sulfoxide) containing 1 mL of iodomethane for 24 hours. The solution was poured onto a horizontal glass plate (9 cm x 9 cm) and allowed to spread naturally. After drying at 80°C, a yellow, transparent ion exchange membrane was obtained. The dried membrane was then subjected to ion exchange in a 1 M sodium chloride solution to obtain a 1 m ion exchange membrane with chloride as the counter ion.

[0179] The results of membrane 1m, whose counterions are iodide ions, were confirmed by nuclear magnetic resonance. Dynamic thermomechanical analysis showed that the Young's modulus and maximum tensile strength of membrane 1m reached 1.8 GPa and 38 MPa, respectively. Atomic force microscopy and small-angle X-ray scattering confirmed that membrane 1m has a microphase separation structure. CO2 adsorption experiments confirmed that it has an ultramicroporous structure with a cumulative pore volume of 0.049 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 1m has good electrochemical performance.

[0180] Example 2 Synthesis of Ionic Polymer 2 and Fabrication of Film 2m

[0181]

[0182] Acid-catalyzed polymerization of diamine monomer 9 (226 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.42 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 11 (0.05 eq, 17.5 mg) was then added and allowed to react until the system gelled. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum-dried to yield 270 mg of polymer, with a theoretical yield of 284 mg and a yield of 95%. The polymer ionization process and membrane laying process were the same as in Example 1, resulting in an ion exchange membrane 2 m.

[0183] The results of membrane 2m, whose counterions are iodide ions, were confirmed by nuclear magnetic resonance. Dynamic thermomechanical analysis showed that the Young's modulus and maximum tensile strength of membrane 2m reached 1.8 GPa and 36 MPa, respectively. Atomic force microscopy and small-angle X-ray scattering confirmed that membrane 2m has a microphase separation structure. CO2 adsorption experiments confirmed that it has an ultramicroporous structure with a cumulative pore volume of 0.041 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 2m has good electrochemical performance.

[0184] Example 3 Synthesis of Ionic Polymer 3 and Fabrication of Film 3m

[0185]

[0186] Acid-catalyzed polymerization of diamine monomer 9 (226 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.4 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 12 (0.05 eq, 17.5 mg) was then added and allowed to react until the system gelled and solidified. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum-dried to yield 273 mg of polymer, with a theoretical yield of 284 mg and a yield of 96%. The polymer ionization process and membrane laying process were the same as in Example 1, resulting in an ion exchange membrane 3 m.

[0187] The results of membrane 3m, whose counterions are iodide ions, were confirmed by nuclear magnetic resonance. Dynamic thermomechanical analysis showed that the Young's modulus and maximum tensile strength of membrane 3m reached 1.8 GPa and 30 MPa, respectively. Atomic force microscopy and small-angle X-ray scattering confirmed that membrane 3m has a microphase separation structure. CO2 adsorption experiments confirmed that it has an ultramicroporous structure with a cumulative pore volume of 0.032 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 3m has good electrochemical performance.

[0188] Example 4 (Synthesis of Ionic Polymer 4 and Fabrication of Film 4m)

[0189]

[0190] Acid-catalyzed polymerization of diamine monomer 13 (212 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.4 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 10 (0.05 eq, 14.5 mg) was then added and allowed to react until the system gelled. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum dried to yield 253 mg of polymer, representing a theoretical yield of 94%. The polymer ionization and membrane-laying process were the same as in Example 1, yielding 4 m of ion exchange membrane.

[0191] The results of membrane 4m, whose counter ions were iodide ions, were confirmed by nuclear magnetic resonance. Atomic force microscopy and small-angle X-ray scattering confirmed that membrane 4m did not have a microphase separation structure. CO2 adsorption experiments confirmed that it had an ultramicroporous structure with a cumulative pore volume of 0.061 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 4m has good electrochemical performance.

[0192] Example 5 Synthesis of Ionic Polymer 5 and Fabrication of Film 5m

[0193]

[0194] Acid-catalyzed polymerization of diamine monomer 14 (276 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.42 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 10 (0.05 eq, 14.5 mg) was then added and allowed to react until the system gelled. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum-dried to yield 314 mg of polymer, with a theoretical yield of 333 mg and a yield of 94%. The polymer ionization process and membrane laying process were the same as in Example 1, resulting in a 5-μm ion exchange membrane.

[0195] The CO2 adsorption experiment confirmed that the membrane 5m has an ultra-microporous structure with a cumulative pore volume of 0.075cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 5m has good electrochemical performance.

[0196] Example 6 Synthesis of Ionic Polymer 6 and Fabrication of Thin Film 6m

[0197]

[0198] Acid-catalyzed polymerization of diamine monomer 15 (290 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.4 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 10 (0.05 eq, 14.5 mg) was then added and allowed to react until the system gelled. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum-dried to yield 331 mg of polymer, with a theoretical yield of 345 mg and a yield of 96%. The polymer ionization process and membrane laying process were the same as in Example 1, resulting in a 6-meter ion exchange membrane.

[0199] The CO2 adsorption experiment confirmed that the membrane 6m has an ultra-microporous structure with a cumulative pore volume of 0.082 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 6m has good electrochemical performance.

[0200] Example 7 Synthesis of Ionic Polymer 7 and Fabrication of Thin Film 7m

[0201]

[0202] Acid-catalyzed polymerization of diamine monomer 16 (284 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.4 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours. Triamine monomer 10 (0.05 eq, 14.5 mg) was then added and allowed to react until the system gelled. The polymerization system was washed with ammonium hydroxide solution and deionized water to remove excess acid. The resulting white polymer was vacuum-dried to yield 327 mg of polymer, with a theoretical yield of 343 mg and a yield of 95%. The polymer ionization process and membrane laying process were the same as in Example 1, resulting in an ion exchange membrane of 7 m.

[0203] The CO2 adsorption experiment confirmed that the membrane 7m has an ultra-microporous structure with a cumulative pore volume of 0.133 cm 3 The conductivity test and the resistance test of the flow battery confirmed that the membrane 7m has good electrochemical performance.

[0204] Example 8 Synthesis of Ionic Polymer 8 and Fabrication of Thin Film 8m

[0205]

[0206] The preparation method of membrane 8m is different from the above steps.

[0207] Acid-catalyzed polymerization of diamine monomer 13 (212 mg, 1 mmol), dimethoxymethane (5 eq, 380 mg), and trifluoroacetic acid (30 eq, 3.4 g) was carried out in a Schlenk flask under nitrogen atmosphere at 0°C for 24 hours with stirring. Triamine monomer 17 (0.05 eq, 15 mg) was then added to continue the reaction. Before the polymerization system gelled and solidified, the reaction solution was evenly coated on a glass plate and continued to react. The trifluoroacetic acid slowly evaporated during this process, forming a polymer film. The resulting membrane was washed with ammonium hydroxide solution and deionized water to remove excess acid, and then vacuum dried to obtain 260 mg of polymer film, with a theoretical yield of 268 mg and a yield of 97%. This polymer was then soaked in a solution of iodomethane in methanol for 24 hours to obtain an ion exchange membrane of 8 m.

[0208] The CO2 adsorption experiment confirmed that the membrane 8m has an ultra-microporous structure with a cumulative pore volume of 0.133 cm 3 The conductivity test and flow battery resistance test confirmed that the membrane m has good electrochemical performance.

[0209] Example 9 Electrochemical performance test of membrane

[0210] Test 1 Four-electrode conductivity test

[0211] The ionic conductivity of the membrane (1 cm × 4 cm) was tested using the four-electrode method.

[0212] like Figure 1 、 Figure 5 、 Figure 7 、 Figure 9 、 Figure 11 、 Figure 13 、 Figure 15 、 Figure 17 The following table shows the conductivity test results for 1m, 2m, 3m, 4m, 5m, 6m, 7m, and 8m ion membranes. The results show that membranes from 1m to 8m exhibit excellent conductivity. At 30°C, the membrane conductivity ranges from 7 to 25mS / cm. At 80°C, the chloride ion conductivity reaches 75mS / cm, a leading level in the industry.

[0213] Test 2: Membrane impedance test

[0214] The impedance of the membrane (3cm×3cm×24µm) was measured using a flow cell and an Autolab electrochemical workstation assembled in the laboratory. The positive electrode consisted of 5mL of a 1M sodium chloride solution containing 0.1M FcNCl, the cathode solution, and the negative electrode consisted of 7.5mL of a 1M sodium chloride solution containing 0.1M BTMAP-Vi, the anode solution.

[0215] like Figure 2 、 Figure 6 、 Figure 8 、 Figure 10 、 Figure 12 、 Figure 14 、 Figure 16 、 Figure 18 The impedance test results of ion exchange membranes with a length of 1m, 2m, 3m, 4m, 5m, 6m, 7m, and 8m are shown. Taking a 1m ion exchange membrane (24um thickness) as an example, the impedance test result is 1.01Ω·cm 2 , which is better than DSV (1.31ohm·cm) under the same conditions 2 ) and AMV film (3.00Ω·cm 2 )impedance.

[0216] Test 3: Flow battery performance test

[0217] The battery performance test of the membrane (3cm×3cm×24um) was carried out using a flow battery and an Autolab electrochemical workstation assembled in the laboratory. 2 ) assembled batteries using carbon cloth as the electrode material. During battery testing, the positive electrode was 5 mL of a 1 M sodium chloride solution containing 0.1 M FcNCl, and the negative electrode was 7.5 mL of a 1 M sodium chloride solution containing 0.1 M BTMAP-Vi.

[0218] result Figure 3 As shown, the cyclic voltammetry test range is 0.4-1.4V, and the maximum power of the battery is 165mW / cm when it is close to 100% charged. 2 (The maximum power of DSV anion membrane under the same conditions is 138mW / cm 2 , the maximum power of AMV is 72mW / cm 2 ). The rate test was conducted at 20mA / cm 2 , 40mA / cm 2 , 60mA / cm 2 , 80mA / cm 2 , 100mA / cm 2 The energy efficiencies were 92.1%, 84.8%, 78.5%, 71.3% and 65.6% respectively, and the coulombic efficiency was always over 99%.

[0219] Test 4: Flow battery cycle stability test

[0220] The main parameters and schematic diagram of the flow battery device are as follows: Figure 19 As shown in the figure, a constant current charge and discharge cycle test was performed using an electrochemical workstation. 2) assembled battery, carbon cloth as electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA / cm 2 The battery was cycled for 500 cycles (5 days) with a charge cutoff voltage of 1.4 V, a discharge cutoff voltage of 0.4 V, and a charge cutoff voltage of 1.4 V. The cathode was a 1 M sodium chloride solution containing 0.1 M FcNCl, and the anode was a 7.5 mL 1 M sodium chloride solution containing 0.1 M BTMAP-Vi.

[0221] Long cycle test results are as follows Figure 4 As shown, in the constant current cycle test of 500 cycles (5 days), the capacity decay is 0.015% per cycle and the coulombic efficiency reaches 100%.

[0222] All documents mentioned in this application are incorporated herein by reference, just as if each document were incorporated herein by reference individually. It should also be understood that after reading the above teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, and that such equivalents also fall within the scope of the claims appended hereto.

Claims

1. A compound represented by the following formula (I), formula (II), or formula (III): in, R 7 Selected from the following group: N, substituted or unsubstituted C1-C10 three-arm alkyl chain, substituted or unsubstituted C6-C10 three-arm aryl, substituted or unsubstituted 6-10 membered three-arm heteroaryl, substituted or unsubstituted C3-C10 three-arm cycloalkyl, substituted or unsubstituted 3-10 membered three-arm heterocycloalkyl, substituted or unsubstituted 4-12 membered three-arm bridged cycloalkyl, substituted or unsubstituted C5-C12 three-arm spirocycloalkyl, substituted or unsubstituted C9-C18 three-arm fused ring aromatic hydrocarbon; R 8 Each is independently selected from the following group: substituted or unsubstituted C1-C10 four-arm alkyl, substituted or unsubstituted C6-C10 four-arm aryl, substituted or unsubstituted 6-10 membered four-arm heteroaryl, substituted or unsubstituted C3-C10 four-arm cycloalkyl, substituted or unsubstituted 3-10 membered four-arm heterocycloalkyl, substituted or unsubstituted 4-12 membered four-arm bridged cycloalkyl, substituted or unsubstituted C5-C12 four-arm spirocycloalkyl, substituted or unsubstituted C9-C18 four-arm fused ring aromatic hydrocarbon; the heteroatom is selected from: N, O, S; The Each is independently selected from the following group: substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 6-20 membered heteroaryl, wherein the aryl or heteroaryl may be a structure selected from the following group: monocyclic aryl, condensed aryl, monoheterocyclic aryl, condensed heterocyclic aryl; The R 1 、R 2 Each independently selected from the following group: None (ie, when R 1 or R 2 There are no chemical bonds between the connected structures), 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, and R 1 、R 2 Not at the same time no or chemical bond; The R 3 、R 4 、R 5 、R 6 Each is independently selected from the following group: 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 amine, carboxyl, phosphate, sulfonic acid; or R 1 and R 2 Together they form a cyclic structure selected from the group consisting of a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted 6-10 membered heteroaryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted 4-12 membered bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, and a substituted or unsubstituted C9-C18 fused ring aromatic hydrocarbon; or R 1 、R 3 and R 5 , or R 2 、R 4 and R 6 Together with the ring atoms separated by it, it forms a cyclic structure selected from the group consisting of a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted 6-10 membered heteroaryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 heterocycloalkyl group, a substituted or unsubstituted 4-12 membered bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, and a substituted or unsubstituted C9-C18 fused ring aromatic hydrocarbon; R 9 Selected from the following group: substituted or unsubstituted C1-C10 alkyl, or the following ionic groups: wherein k and j are each independently selected from 1, 2, 3, 4, 5, 6, 7 or 8; R 10 、R 11 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 group: -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ;Q - Select 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 following group: substituted or unsubstituted C1-C10 alkyl; The X - Select from the following group: F - 、Cl - Br, I - OH - 、OAc - 、OTf - ,OTs - 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ; Unless otherwise specified, the substitution refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the following groups: halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, hydroxyl, amino, carboxyl; the heterocycloalkyl or heteroaryl refers to a group containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen.

2. The compound of formula (I), formula (II), or formula (III) according to claim 1, wherein The R 7 Selected from the following group: N, substituted or unsubstituted C1-C10 three-arm alkyl, substituted or unsubstituted C6-C10 three-arm aryl, substituted or unsubstituted 6-10 membered three-arm heteroaryl, substituted or unsubstituted C9-C18 three-arm condensed aromatic hydrocarbon; or a complex group composed of any two or more of the above groups; The R 8 Selected from the following groups: substituted or unsubstituted C1-C10 four-arm alkyl, substituted or unsubstituted C6-C10 four-arm aryl, substituted or unsubstituted 6-10 membered four-arm heteroaryl, substituted or unsubstituted C9-C18 condensed ring aromatic hydrocarbon; or a complex group composed of any two or more of the above groups.

3. The compound of formula (I), formula (II), or formula (III) according to claim 1, wherein The A substituted or unsubstituted structure selected from the following group:

4. The compound of formula (I), formula (II), or formula (III) according to claim 1, wherein The R 1 、R 2 are each independently selected from the following group: none, a chemical bond, a substituted or unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group containing 1-4 heteroatoms selected from oxygen, sulfur and nitrogen, a substituted or unsubstituted C4-C12 bridged cycloalkyl group, a substituted or unsubstituted C5-C12 spirocycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, and R 1 、R 2 Not at the same time is none or chemical bond.

5. The compound of formula (I), formula (II), or formula (III) according to claim 1, wherein The compound has a structure selected from the following table:

6. The compound of formula (I), formula (II), or formula (III) according to claim 1, wherein The compound is prepared by the following method: Copolymerizing a formaldehyde source monomer, one or more compounds selected from the group consisting of Formulas A-1, A-2, A-3, and A-4 with one of the compounds of Formulas A1, A2, or A3 to obtain the compound of claim 1, 7. A method for preparing the compound according to claim 1, characterized in that: The method comprises the steps of: (i-1) in the presence of trifluoroacetic acid, carrying out an acid-catalyzed polymerization reaction using a diamine monomer selected from one or more of Formulas A-1, A-2, A-3 and A-4, a formaldehyde source monomer, and trifluoroacetic acid; (i-2) After step (i-1), add A1 or A2 and continue the reaction until the system gels and solidifies to form a polymer system; (i-3) post-treating the polymerization system obtained in step (i-2) to perform quaternization to obtain a quaternized polymer solution; (i-4) subjecting the quaternized polymer solution obtained in step (i-3) to ion exchange to obtain the compound of formula I or formula II according to claim 1; or (ii-1) acid-catalyzed polymerization of a diamine monomer selected from one or more of formulas A-1, A-2, A-3, and A-4 with a formaldehyde source monomer in the presence of trifluoroacetic acid; (ii-2) After step (ii-1) is completed, A3 is added to form a polymerization system, and the system is coated on a plate to continue the reaction before the gel solidifies to obtain a polymer film material. (ii-3) taking the polymer film material obtained in step (ii-2) and post-treating it to obtain a polymer film; (ii-4) The polymer film obtained in step (ii-3) is immersed in a methanol solution of iodomethane to react and obtain the compound of formula III according to claim 1.

8. The preparation method according to claim 7, wherein The formaldehyde source monomer is selected from the following group: formaldehyde solution, paraformaldehyde, hexamethylenetetramine, trioxane and dimethoxymethane.

9. A use of the compound according to claim 1, characterized in that, Used to prepare an ion exchange membrane; wherein the preparation method of the ion exchange membrane comprises the steps of: (1) providing the compound of claim 1 and spreading it on a plate; (2) Drying the plate of step (1) to obtain an ion exchange membrane.

10. The use according to claim 9, characterized in that The ion exchange membrane is used in an aqueous liquid flow battery.

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