KR101750412B1 - Anion conducting body comprising anion conducting block copolymer having polyphenylene-based hydrophilic main chain, preparation method and use thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to an anionic ion conductor comprising an anionic conductive block copolymer having a polyphenylene-based hydrophilic main chain structure, a method for producing the same, and a use thereof, wherein the hydrophilic domain constituting the main chain is composed of a carbon- Anionic ion conductors exhibiting excellent dimensional stability and chemical stability as well as anion transferring selectively anions are provided, a method for producing the same, and uses thereof. In particular, the anion ion conductor according to the present invention exhibits excellent Coulomb efficiency and can be applied to an electrolyte membrane or an electrode for a fuel cell, because it has an advantage of improving the performance of the device when it is applied as an anion conductor.

Description

TECHNICAL FIELD The present invention relates to an anionic ionic conductor comprising an anionic conductive block copolymer having a polyphenylene-based hydrophilic main chain structure, a method for producing the same,

The present invention relates to an anionic ion conductor comprising an anionic conductive block copolymer having a polyphenylene-based hydrophilic main chain structure, a method for producing the same, and a use thereof.

(PEMFC), a direct methanol fuel cell (DMFC), a direct ethanol fuel cell (DEFC), a reverse electrodialysis (RED) In an energy storage system such as a renewable energy and a redox flow battery (RFB), the ion conductive polymer membrane is a core chemical material that affects performance and durability. However, since it does not have a related technology in Korea at present, And all depend on imports.

Redox Flow Battery (RFB) is a secondary battery that can store and store energy for a long time by repeated charging and discharging by electrochemical reversible reaction of electrolyte. The stack and electrolyte tanks, which depend on the capacity and output characteristics of the battery, are independent of each other, so that the battery design is free and the installation space is limited.

The redox flow battery has a load leveling function that can cope with the sudden increase in power demand installed in a power plant, a power system, or a building, and has a function to compensate or suppress the power failure or the instantaneous undervoltage. It is an energy storage technology and suitable for large-scale energy storage.

These redox flow cells consist of two separate electrolytes. One stores the electroactive material in the negative electrode reaction and the other stores the positive electrode reaction. In an actual redox flow cell, the electrolyte reaction is different between the positive electrode and the negative electrode, and there is a flow of the electrolytic solution, so a pressure difference occurs between the positive electrode and the negative electrode. The reaction of the positive and negative electrode electrolytes in the entire vanadium-based redox flow battery, which is a typical redox flow battery, is as follows.

Therefore, a separation membrane with improved physical and chemical durability is required to overcome the pressure difference between both electrodes and to exhibit excellent cell performance even when charging and discharging are repeated. As a separator (electrolyte membrane) in a redox flow cell, a cation exchange material or an anion exchange material is generally used. Generally, a cation exchange material which is easier to manufacture is used, but an anion exchange material is more advantageously applied to control the movement of water in the active material or electrolyte. Nevertheless, its use is restricted due to the high difficulty of material reconstruction and non-diversity of materials.

Fuel cells are energy conversion devices that convert the chemical energy of fuels directly into electrical energy. They are being developed as a next generation energy source with high energy efficiency and eco-friendly characteristics with less pollutant emissions.

Generally, a fuel cell includes an anode that supplies hydrogen ions and electrons from a fuel such as hydrogen or methanol, and a cathode that can supply oxygen.

The principle of generating electricity in a fuel cell is that when fuel is supplied through a fuel electrode, the fuel is divided into hydrogen ions and electrons, hydrogen ions combine with oxygen supplied from the air electrode through the electrolyte membrane to become water, The electrons separated from the cathode generate an electric current through the external circuit, and the electrochemical reaction of the reverse reaction of electrolysis of water proceeds to generate electricity, heat, and water.

Fuel cells include polymer electrolyte fuel cells, direct methanol fuel cells, direct ethanol fuel cells, direct borohydride fuel cells (DBFCs), and solid alkaline fuel cells (SAFCs).

Among the above fuel cells, the polymer electrolyte fuel cell, the direct methanol fuel cell, and the direct ethanol fuel cell employ a cation exchange membrane which is a cation or a proton conductive electrolyte membrane as an electrolyte. However, in contrast to the solid alkaline fuel cell, Anion exchange membrane should be employed. On the other hand, a direct boron hydride fuel cell can use both a cation exchange membrane and an anion exchange membrane.

Specifically, a solid alkaline fuel cell mainly uses an aqueous solution of potassium hydroxide as an electrolyte and uses hydrogen as a fuel. Solid alkaline fuel cells are significantly different from other fuel cells in power generation methods. Specifically, as shown in the following reaction formula, oxygen supplied from the air to the battery reacts with water in the air electrode to generate hydroxide ions (OH ^- ). The hydroxide ions migrate to the anode and produce a catalytic reaction with hydrogen to produce water, The former moves to the external circuit.

Cathode

O ₂ + 2H ₂ O + 4e ^- ? 4OH ^-

Anode

2H ₂ + 4OH ^- ? 4H ₂ O + 4e ^-

On the other hand, a direct boron hydride fuel cell uses sodium borohydride or boron hydride as a fuel, and the oxygen supplied from the air to the cell reacts with water in the air electrode to generate hydroxide ions (OH < ^- > This hydroxide ion moves to the anode and catalyses the reaction with hydrogen to produce water, and the electrons move to an external circuit.

Cathode

2O ₂ + 4H ₂ O + 8e ^- ? 8OH ^-

Anode (when sodium boron hydride is used as fuel)

NaBH ₄ + 8OH ^{- -} > NaBO ₂ + 6H ₂ O + 8e ^-

Accordingly, the solid alkaline fuel cell and the direct boron hydride fuel cell can be driven by employing an anion exchange membrane, which is a hydroxide ion conductive electrolyte membrane, as described above.

The fuel cell employing the anion exchange membrane is characterized in that it can use a non-precious metal or an opaque metal catalyst for the electrode as compared with the fuel cell employing the cation exchange membrane, and thus the price can be reduced.

On the other hand, the currently used electrolyte membrane is a perfluorocompound cation exchange membrane represented by Nafion. This is very good in performance and durability, but has the disadvantage that it is very expensive and the crossover of the fuel is severe. Existing anion exchange membranes include FAP, which is a perfluorinated anion exchange membrane of Puma Tech, Germany, VPX, which is a hydrocarbon-based anion exchange membrane, and AMX of Tokuyama, Japan. However, these anion exchange membranes are not only expensive but also have low performance.

An object of the present invention is to provide an anionic ion conductor including an anion conductive block copolymer having excellent physical properties and anion conductivity capable of being applied to an anion exchange membrane and the like, a method for producing the same, and a use thereof.

The first aspect of the present invention provides an anionic ion conductor for selective migration of an anion including an anionic conductive polymer represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

A is a single bond or an electron withdrawing group which is - (C = O) -, - (P = O) -, -CF ₂ -, - (C (CF ₃ ) ₂ ) - or - (SO ₂ ) -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;

B is -O-, -S-, -NH- or -NR ₂₅ - as a single bond or electron donor group, wherein R ₂₅ is an alkyl group;

Z is an anion exchange functional group, an amphoteric ion exchange functional group or a combination thereof;

W is hydrogen;

a and b are each an integer belonging to 1 to 10;

c is an integer belonging to 1 to 5;

1 is an integer belonging to 1 to 10,000;

이며, 이때 G는 단일결합 또는 전자끌게기로서 -(C=O)-, -(P=O)-, -CF₂-, -(C(CF₃)₂)- 또는 -(SO₂)-이고, J는 전자주게기로서 -O-, -S-, -NH- 또는 -NR₂₅-이며, 이때 R₂₅는 알킬기이고;D is a single bond or -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group, or

And, wherein G is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - And J is an electron donor group such as -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;

이며, 이때 P는 단일결합 또는 전자끌게기로서 -(C=O)-, -(P=O)-, -CF₂-, -(C(CF₃)₂)- 또는 -(SO₂)-이고;Wherein Ar 'is an unsubstituted or substituted group selected from the group consisting of a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, a cyano group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group; or

And, where P is a bond or an electron withdrawing single group - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - ego;

이며, 이때 P'는 단일결합 또는 전자끌게기로서 -(C=O)-, -(P=O)-, -CF₂-, -(C(CF₃)₂)- 또는 -(SO₂)-이고;Ar "refers to an unsubstituted or substituted group containing one or more oxygen, nitrogen or sulfur atoms in the chain, such as a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group;

And, where P 'is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ -ego;

Wherein P and P 'are the same or different from each other;

E is -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group;

R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with at least one halogen, an allyl group, a cyano group, an aryl group, optionally containing at least one oxygen, nitrogen or sulfur atom A perfluoroalkylaryl group, a perfluoroaryl group or an -O-perfluoroaryl group;

q is an integer of 0 or 1;

p is an integer from 0 to 1000;

n is an integer from 1 to 10,000;

X and X 'are each independently a halogen atom.

Preferably, E in the anionic conducting polymer included in the anion ion conductor is -O-; and p may be an integer of 1 to 50.

A second aspect of the present invention is the method for manufacturing the anion ion conductor according to the first aspect,

A first step of preparing a hydrophilic monomer represented by the following formula (2);

A second step of preparing a hydrophobic monomer represented by the following formula (3);

A third step of mixing the hydrophilic monomer and the hydrophobic monomer to form a block copolymer by a colon coupling reaction;

A fourth step of halomethylating the block copolymer;

A fifth step of molding the halomethylated block copolymer into a predetermined shape; And

And a sixth step of partially or completely replacing the halogen functional group of the formed halomethylated block copolymer with an anion exchangeable functional group, an amphoteric ion-exchange functional group, or a combination thereof.

(2)

(3)

In this formula,

A, B, W, a, b, D, Ar ', Ar ", E, R 1 to R _4, q, p, X and X' are as defined in the first aspect.

A third aspect of the present invention provides an electrolyte membrane comprising an anion ion conductor according to the first aspect.

A fourth aspect of the present invention provides a fuel cell including the anion ion conductor according to the first aspect in an electrolyte membrane or an electrode.

A fifth aspect of the present invention provides an oxidized flow cell comprising an anion ion conductor according to the first aspect in an electrolyte membrane.

A sixth aspect of the present invention provides a water treatment apparatus comprising an anion ion conductor according to the first aspect in an electrolyte membrane.

A seventh aspect of the present invention provides the anionic conductive polymer represented by the above formula (1).

An eighth aspect of the present invention provides a binder composition for an electrode comprising the anionic conductive polymer according to the seventh aspect.

Hereinafter, the present invention will be described in detail.

Conventionally, most ionic conductors are mainly cationic ionic conductors. However, in order to develop a fuel cell or the like employing an anion exchange membrane, development of an anion ion conductor applicable to an anion conductive electrolyte membrane is required. Existing anion exchange materials include FAP and VPX membranes from Puma Tech, Germany. They are not only very expensive, but also have very low ionic conductivity due to their specific properties for oxidation-flow cells, making them difficult to apply to applications such as fuel cells.

The difficulty in developing such materials is due to the high degree of synthesis of anion conductors. In the case of anionic conductors, there are more side reactions during synthesis than in cationic conductors, and the hydration number (number of water molecules in one ion exchanger) of the ion exchanger is so large that the improvement of the molecular weight during synthesis of the polymer is limited, It is difficult to do. Unlike the cation exchange materials, which can easily produce ion-exchange materials through the synthesis of monomers having an ion-exchange group by polymer synthesis reaction between them, the synthesis process of introducing an ion-exchange group after synthesizing the main chain is required, It restricts the synthesis route of the exchange material and increases the degree of difficulty. In addition, the anion-exchange material has a long and complicated reaction route due to introduction of an ion-exchange group through amination reaction through chloromethylation reaction or bromination reaction, compared with a cationic material in which an ion-exchange group is directly introduced into a main chain and a monomer through a sulfonation reaction . Especially, the chloromethylation reaction through the friedel-crafts acylation reaction is very sensitive to the temperature and reaction time conditions due to the crosslinking reaction due to the side reaction. Even though the structure of the main chain is the same, the process of introducing the ion exchange material of the cation exchange material and the anion exchange material is completely different. In the case of the anion exchange material, various conditions such as the temperature and the reaction time must be considered. .

On the side of the membrane, the cation exchange material can be stored in the polymer powder due to the relatively low ion exchange period interaction, and it is easy to prepare the polymer solution again. However, in the case of anion exchange material, due to the interaction of the high ion exchange period, the gelation proceeds easily in the solution process after the ion exchange, and the film formation itself becomes impossible.

In the present invention, unlike the cation exchange material, anion exchange material was prepared by introducing the ion exchanger after the film formation through the heterogeneous ion exchange of the chloromethylated polymer. The present invention provides an anion exchange material based on a low-cost hydrocarbon-based material, that is, an anion ion conductor. The anion ion conductor according to the present invention exhibits a very excellent ion conductivity as compared with the competitive material even in the case of having a Cl ^- counter ion, so that it can be applied to various applications. In addition, since the anion ion conductor according to the present invention selectively moves only anions, crossover of the active material can be basically prevented in an oxidation flow cell (RFB) using a cationic active material, and even when applied to a fuel cell, This is the direction opposite to the direction of the movement of the fuel, thereby preventing the crossover of the fuel. In addition, a fuel cell employing an anion exchange membrane can advantageously use a low-cost metal catalyst in addition to expensive platinum, thereby contributing to a reduction in the overall system price.

As a specific embodiment, in the present invention, as shown in Fig. 1, a block copolymer composed of a hydrophilic block and a hydrophobic block, particularly a polyphenylene-based backbone structure having excellent physical / chemical stability, is introduced into a hydrophilic block to provide the durability . More specifically, the anionic ion conductor according to the present invention has a multiphenyl pendant structure, is composed of a carbon-carbon bond and has a more rigid structure, and its terminal is an anion exchange functional group, amphoteric ion exchange (-O-), a sulfide bond (-S-), an amine (-S-), an amine bond (-S-), an amine bond And a polyarylene-based hydrophobic block containing a flexible bonding structure such as a polyether-ether bond, a polyetherketone, and a polyether-ether bond, and has excellent dimensional stability and chemical stability, and has an anion conductivity higher than that of a conventional commercial anion- efficiency is excellent.

In other words, the anion ion conductor according to the present invention is characterized in that the hydrophilic domain constituting the main chain is composed of a carbon-carbon bond excluding an ether bond and is excellent in dimensional stability, and the neighboring phenyl ring substituted with an anion- (-O-), sulfide bond (-S-), and / or amine bond described above, the chemical stability against various radicals is excellent. When a block copolymer containing such a hydrophilic block as a part is used, it is possible to provide an electrolyte membrane for a battery which exhibits high ionic conductivity and at the same time has excellent chemical stability. In addition, the hydrophilic block may be designed to form a dense and locally arranged structure of the exchanger that selectively transfers the anion, thereby causing effective phase separation of the hydrophilic domain and the hydrophobic domain. On the other hand, the hydrophobic block can impart flexibility to a polymer by including a polyarylene series as a skeleton containing an ether bond (-O-), a sulfide bond (-S-) and / or an amine bond. In particular, the anion ion conductor according to the present invention has excellent anionic conductivity and exhibits excellent coulombic efficiency, and thus has an advantage that the performance of the device can be improved when applied as an anionic conductor. The present invention is based on this.

According to the present invention, a hydrophilic block has a structure of a polyphenyl pendant having a phenylene repeating unit as a backbone, and has at least one anion-exchange functional group and / or amphoteric ion exchange May be a polymer composed of a monomer having at least one aryl group substituted with a functional group.

According to the present invention, "multiphenyl pendant" may be a substituent comprising a plurality of phenyl groups. For example, a phenyl ring containing one or more substituted or unsubstituted phenyl, naphthalene or heteroatom in one phenyl ring may be a further substituted bulky substituent.

The hydrophilic block can be imparted with anionic conductivity through an introduced anion-exchangeable functional group and / or an amphoteric ion-exchangeable functional group.

The anion-exchange functional group is _{-NH 3 T, -NR'H 2 T,} -NR '2 HT, -NR' 3 T, -PR '3 T or -SR' ₂ T, or -C ₅ H ₅ NHT and ( R 'is alkyl or aryl and T is a hydroxide anion, a bicarbonate anion, a chloride anion or a sulfate anion), the amphoteric ion-exchange functional group may be betaine or sulphobetaine. More specifically, the anion exchangeable functional group may be an anion exchange functional group selected from an amine group, an ammonium group, an amino group, an imine group, a sulfonium group, a phosphonium group, a pyridyl group, a carbazolyl group and an imidazolyl group, Exchangeable functional group. Specific examples of anion-exchangeable functional groups include, but are not limited to, trimethylamine, triethylamine, dimethylamine, diethanolamine, creehexylamine, dihexylmethylamine, hexyldimethylamine, aminoalkylphosphonized compounds, iminodiacetate or N- Carmine, and the like, and one or more of the above ion exchange functional groups can be selected. The selection of the anion exchangeable functional group also depends on the application and is not limited to the above examples as long as it is a functional group capable of exchanging anions.

On the other hand, since the anion-exchangeable functional groups and / or amphoteric ion-exchangeable functional groups are hydrophilic, if the proportion of these hydrophilic blocks in the polymer is high, the water resistance of the electrolyte membrane produced therefrom deteriorates and the swelling of the electrolyte membrane It may be difficult to satisfy the physical properties of the electrolyte membrane required for driving a device such as a fuel cell due to mechanical strength and lowered degree of integration. The polymer of the present invention can provide a mechanical strength by including a hydrophobic block.

In one embodiment, E is -O- in the anion-conducting polymer; and p may be an integer of 1 to 50. That is, the hydrophobic block may contain an ether bond, and the hydrophobic block (-Ar'-E-Ar "-E-) may have 1 to 50 bonded units. This is because the physical properties can be optimized.

In the present invention, "alkyl" is a saturated linear or branched structure of from 1 to 20 carbon atoms, or a saturated cyclic structure consisting of from 3 to 20 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl (isopropyl), n-butyl, i-butyl, t-butyl, n-dodecyl, cyclopropyl or cyclohexyl groups do. And may contain one or more heteroatoms selected from oxygen, sulfur and / or nitrogen in the cyclic structure.

In the present invention, "aryl" means a functional group or substituent derived from an aromatic ring compound. The cyclic compound may be composed of only carbon atoms and may include one or more hetero atoms selected from oxygen, sulfur and / or nitrogen. For example, the carbon-only aryl group includes phenyl, naphthyl, anthracenyl and the like. Examples of the aryl group containing a hetero atom include thienyl, indolyl, Pyridinyl, and the like. The heteroatom-containing aryl may be heteroaryl, but in the present invention, it is aryl.

In the present invention, the term "perfluoroalkyl group", "perfluoroaryl group", "-O-perfluoroaryl group", and perfluoroalkylaryl group ( perfluoroalkylaryl "means alkyl, aryl and -O-aryl in which all of the hydrogen atoms thereof are substituted by fluorine atoms (F).

In the present invention, "halogen" is an atom selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

(1): the total number of monomers forming the hydrophobic block (n) = 0.1 (1), the number of the monomers forming the hydrophobic block : 1 to 100: 1. For example, when the molar ratio is less than 0.1: 1, ionic conductivity is almost zero. When the molar ratio is 100: 1 or more, the polymer is dissolved in water and can not act as an actual separator. More preferably 0.1: 1 to 50: 1, and even more preferably 0.1: 1 to 30: 1.

Preferably, the anion-conducting polymer according to the present invention may have a number-average molecular weight (Mw) of 10,000 to 1,000,000 or a molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000. have. When the molecular weight is low, for example, when it is 10,000 or less, film formation is difficult, the moisture content is increased, and it is easily decomposed by the attack of radical, so that conductivity and durability may be decreased. On the other hand, in the case where the molecular weight is high, for example, 1,000,000 or more, the rapidly increasing viscosity may make the preparation of the polymer solution and molding into a film difficult, making the film production process impossible.

Since the weight average molecular weight and the viscosity average molecular weight are similar to each other, the intrinsic viscosity of the polymer is measured to predict the molecular weight in the specific examples of the present invention. The molecular weight can be measured by gel permeation chromatography (GPC). However, when anion-exchangeable functional groups and / or amphoteric ion-exchange functional groups are substituted like the polymer of the present invention, The viscosity was measured and the molecular weight was predicted.

The anion ion conductor according to the present invention may be a molded body formed from a resin composition containing an anionic conductive polymer. The molded body may be an electrolyte membrane, but is not limited thereto. Specifically, the electrolyte membrane may be an electrolyte membrane for an oxidative flow cell, an electrolyte membrane for a fuel cell, an electrolyte membrane for an electrolytic solution, an electrolyte membrane for electrodialysis, or an electrolyte membrane for a reverse electrodialysis. The electrolyte membrane for a fuel cell may be applied to a solid alkaline fuel cell or a direct borohydride fuel cell. Meanwhile, the anion ion conductor according to the present invention may be an electrode for a fuel cell including the anion conductive polymer according to the present invention as a binder.

The term "electrolyte membrane" of the present invention is a semipermeable membrane called anion exchange membrane. It selectively transports and / or transfers only anions and is impermeable to gases such as oxygen or hydrogen. Is introduced into a membrane-electrode assembly (MEA) of an anion exchange membrane fuel cell or an anion exchange membrane electrolyzer to separate the reactants and to transfer and / or transfer anions It does the main function. Specifically, when used as a membrane-electrode assembly in a fuel cell, the polymer membrane transmits anions but not proton.

 These electrolyte membranes should have preferential properties such as ionic conductivity, impermeability to fuel and thermal stability.

Therefore, the electrolyte membrane must exhibit a high ionic conductivity to be used in a fuel cell, and it can be operated at a high temperature of 100 ° C or more. Also, when the membrane-electrode assembly is manufactured by high- And should exhibit an excellent barrier property against a fuel which has a high chemical stability so that it is not decomposed even under extreme conditions such as strong acids and at the same time anion is transferred but the raw material is prevented from penetrating.

The term "redox flow battery" of the present invention means that an electrolyte containing an electroactive species flows through an electrochemical cell, which reversibly converts chemical energy into electricity, A rechargeable fuel cell, which is a type of flow cell, is a reversible fuel cell in which all electro-active components are dissolved in an electrolyte. Gravity feed systems are used, but mainly the additional electrolyte is stored externally, typically in a separate tank, and is pumped through the cells of the reactor. Flow cells can be quickly recharged by replacing the electrolyte solution (in a manner similar to replenishing the fuel tank of an internal combustion engine) while at the same time recovering the spent material for re-energization. In such a redox flow battery, the energy of the cell is determined by the electrolyte volume, e.g., the tank size, and the power is determined by the electrode area, e.g., the reactor size, so that the energy is decoupled completely from the power as with other fuel cells.

As shown in FIG. 2, the redox flow battery is different from other batteries in that an electroactive species exists in the form of an aqueous solution that is not a solid, and the redox flow cells are oxidized / reduced It has a mechanism to store energy by reaction. The positive electrode electrolyte and the negative electrode electrolyte for causing the above-described reaction are stored in separate storage tanks (not shown), respectively, and are introduced into the cell housing 51 through the electrolyte inflow ports 31 and 41 formed in the cell housing 51 And has a circulation system that contacts the anode 21 and the cathode 22 to cause a reaction and then flows out through the respective electrolyte outlets 32 and 42. The battery is discharged by connecting an electric load to an external circuit including an electric load to allow a current to flow, and conversely, an external power source is connected to the battery to allow the electric current to flow. In general, a cathodic electrolyte is charged when the redox couple is oxidized to the higher of the two states, and is discharged when the redox is reduced to the lower state. In the negative electrode electrolyte solution, the opposite phenomenon appears.

As described above, most redox flow cells are composed of two separate electrolytes. One stores the electroactive material in the negative electrode reaction and the other stores the positive electrode reaction. At this time, the negative electrode is defined as the anode and the positive electrode is defined as the cathode in discharging to prevent confusion. The charge will be reversed. Fresh or used electrolytes can be circulated and stored in a single storage tank. Or the concentration of the electroactive material can be individually adjusted. An ion exchange membrane is used as a separation membrane (separation membrane) in order to prevent mixing of electroactive species which may cause chemical breakdown.

The term "separation membrane" of the present invention refers to an ion exchange membrane introduced to prevent mixing of electroactive species in the redox flow cell, and a common counter ion carrier ) Passes through the separation film. In an actual redox flow cell, the electrolyte reaction is different between the positive electrode and the negative electrode, and there is a flow of the electrolytic solution, so a pressure difference occurs between the positive electrode and the negative electrode. Therefore, it is preferable that the separation membrane has excellent physical strength so as not to be broken by such a pressure difference.

The method for producing an anion ion conductor according to the present invention may comprise the following steps as described above:

A first step of preparing a hydrophilic monomer represented by the following formula (2);

A second step of preparing a hydrophobic monomer represented by the following formula (3);

A third step of mixing the hydrophilic monomer and the hydrophobic monomer to form a block copolymer by a colon coupling reaction;

A fourth step of halomethylating the block copolymer;

A fifth step of molding the halomethylated block copolymer into a predetermined shape; And

A sixth step of partially or completely replacing the halogen functional group of the formed halomethylated block copolymer with an anion exchangeable functional group, an amphoteric ion-exchange functional group, or a combination thereof;

(2)

(3)

In this formula,

A, B, W, a, b, D, Ar ', Ar ", E, R 1 to R _4, q, p, X and X' are as defined in the first aspect.

The first step is a step of preparing a hydrophilic monomer represented by the above formula (2) to form a hydrophilic block.

The method for producing an ion conductive polymer according to the present invention is characterized in that a hydrophilic block and a hydrophobic block are not separately prepared. The general method of producing a block copolymer is such that a polymer forming each block is separately prepared and reacted to prepare a block copolymer. However, according to the above production method, the hydrophilic block and the hydrophobic block portion may be prepared by directly mixing the monomer forming the hydrophilic block with an oligomer (for example, when p is an integer of 1 to 10) or a polymer (For example, when p is an integer of 11 to 1000), a block copolymer containing a hydrophilic block and a hydrophobic block can be prepared. For example, even if a hydrophilic monomer is reacted with an oligomer forming a hydrophobic block, hydrophilic monomers having similar physical properties are highly likely to interact with each other, so that the hydrophilic polymer is preferentially reacted to form a hydrophilic polymer. At the same time, oligomers forming a hydrophobic block preferentially react To form a hydrophobic polymer, and then the hydrophilic polymer and the hydrophobic polymer bind to each other to form a block copolymer. Accordingly, the manufacturing method can eliminate the process of manufacturing the hydrophilic block and the hydrophobic block by the separate process, thereby reducing the cost and improving the yield.

The hydrophilic monomer of the first step may be synthesized or commercially available and purchased from the market.

The second step is a step of preparing the hydrophobic monomer represented by the above formula (3) to form a hydrophobic block.

The second step may include a step 2-1 of reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) under a K ₂ CO ₃ catalyst:

[Chemical Formula 4]

[Chemical Formula 5]

In this formula,

R ₉ to R ₂₄ , P and P 'are as defined in the first aspect,

K ₁ to K ₄ each independently represent an amino group substituted with a halogen, a hydroxyl group, a thiol group, or an unsubstituted or alkyl group.

The second step may further include a step 2-2 of reacting the product of the second stage-1 and the compound represented by the following formula (6) after the stage 2-1.

[Chemical Formula 6]

In this formula,

R ₅ to R ₈ , G and K are the same as defined in the first aspect,

K ₅ to K ₆ are each independently an halogen group, a hydroxyl group, a thiol group, or an amine group substituted with an unsubstituted or alkyl group.

The reaction of steps 2-1 and 2-2 may be carried out by a nucleophilic substitution reaction between a highly reactive halogen, a hydroxyl group, a thiol group, or an amine group substituted in the reactant. Since the resulting compound also has a halogen, a hydroxyl group, a thiol group or an amine group having high reactivity at the terminal thereof, it is necessary to control the mild reaction conditions and time so as not to excessively polymerize.

In the second step (Steps 2-1 and 2-2), dimethylacetamide, toluene or a mixed solvent thereof may be used. The reaction may be carried out at 100 to 160 ° C for 2 to 24 hours And preferably in an inert gas atmosphere.

The first to second steps are not performed using the products of the respective steps but are performed separately from each other in order to produce the respective products from separate reactants. In addition, precipitation, filtration and / or washing procedures can be performed.

In the third step, the hydrophilic monomer prepared in the first step and the hydrophobic monomer prepared in the second step are mixed to form a block copolymer by a colon coupling reaction.

In the present invention, "monomer" may mean a molecule capable of forming a polymer by chemically bonding with another molecule. The hydrophilic monomer may be in the form of a single molecule, and the hydrophobic monomer may be an oligomer such as a trimer previously synthesized or obtained (for example, when p is an integer of 1 to 10) or a polymer (for example, p is 11 to 1000 Lt; / RTI > may be in the form or polymer form.

The colon coupling reaction in the third step may be carried out by reacting the monomer prepared in the first or second step having at least one halogen element as a reactor at both ends thereof with a metal to be reduced with a catalyst to form a carbon- Thereby producing a polymer. As the metal to be reduced, zinc (Zn), magnesium (Mg), manganese (Mn), aluminum (Al) or calcium (Ca) may be used. As the catalyst, 2,2'- -bipyridine) or triphenylphosphine (PPh _3, triphenylphosphine; TPP) of _{NiBr 2, NiCl 2, Br 2} , (acac) 2 · H 2 O, (OOCCH 3) · 4H 2 O, I 2 · 6H 2 O Or with other halide salts (F <Cl <Br <I). Preferably dimethylacetamide (DMAc) as a solvent at 60 to 100 ° C while stirring with NiBr ₂ , triphenylphosphine and zinc for 6 to 10 hours. Further, after the formation of the block copolymer, the step of removing zinc, the step of washing, or the step of drying may be further included.

The fourth step is a step of halomethylating the block copolymer to introduce the halogen functional group as a functional group for substituting the anion-exchange functional group and / or the amphoteric ion-exchange functional group in the sixth step in the block copolymer to be.

The fourth step may be performed by reacting the block copolymer obtained in the third step with halomethyl methyl ether.

The halomethylation reaction in the fourth step may be performed at 30 to 60 ° C for 12 to 60 hours, preferably under an inert gas atmosphere.

In the fourth step, the solvent may dissolve the polymer, and any solvent may be used as long as it does not inhibit the chloromethylation reaction of the polymer. Specifically, 1,1,2,2-tetrachloroethane (TCE), 1,2-dichloroethane (DCE), or a mixed solvent thereof may be used as the solvent.

The fifth step is a step of molding the halomethylated block copolymer into a desired shape to obtain a molded article.

The molding of the fifth step may be carried out by molding the resin composition containing the polymer of the previous step into a fiber or film form by any method such as extrusion, spinning, rolling or casting. The resin composition may further contain various additives such as an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a cross-linking agent, a defoaming agent, and a dispersant, if necessary.

Specifically, the polymer of the previous step is dissolved in a solvent, poured into a silicone mold having a predetermined size, and dried at 60 to 100 ° C, preferably 70 to 90 ° C for 12 to 36 hours, preferably 18 to 30 hours to obtain a film.

For example, a resin composition containing a polymer of the previous step may be molded to produce an electrolyte membrane. Specifically, the polymer is dissolved in a solvent such as N-methylpyrrolidone (NMP), dimethylformamide, dimethylsulfoxide or dimethylacetamide, the solution is poured into a plate such as a glass plate, To obtain a film having a thickness of several to several hundreds of μm, preferably 10 to 120 μm, more preferably 50 to 100 μm, and then desorbing from the plate. The above-mentioned solvent is only illustrative, and the scope of the present invention is not limited thereto. Conventional organic solvents may be used as long as they dissolve the polymer and can be evaporated under the drying condition. Specifically, the same organic solvent as that used in the preparation of the polymer may be used.

The sixth step is a step of obtaining an anion ion conductor by partially or completely replacing the halogen functional group of the formed halomethylated block copolymer with an anion exchangeable functional group, an amphoteric ion exchangeable functional group, or a combination thereof.

In the sixth step, the formed halomethylated block copolymer is reacted with NH ₄ T, NR'H ₃ T, NR ' ₂ H ₂ T, NR' ₃ HT, PR ' ₃ HT or SR ' ₂ HT or C ₅ H ₅ NH ₂ T wherein R' is alkyl or aryl and T is a hydroxide anion, a bicarbonate anion, a chloride anion or a sulfate anion, betaine as an amphoteric ion- Sulfobetaine, or a combination thereof.

According to the production method of the present invention, it is possible to perform ion exchange through an inhomogeneous method using an organic solvent, which not only improves the ion exchange degree but also simplifies the manufacturing process compared to the process of producing the membrane again after ion exchange .

The anion ion conductor according to the present invention can be produced at a lower cost than the perfluorocompound cation exchange membrane and can significantly reduce the crossover of the fuel and the active material depending on the field of application so that the performance and lifetime of the entire system can be improved . In addition, when used as an electrolyte membrane in a fuel cell, it is possible to use an inexpensive metal catalyst in addition to expensive platinum, thereby significantly reducing the system cost. In particular, the anion ion conductor according to the present invention exhibits excellent Coulomb efficiency and can be applied to an electrolyte membrane or an electrode for a fuel cell, because it has an advantage of improving the performance of the device when it is applied as an anion conductor.

1 is a diagrammatic representation of a block copolymer according to the present invention comprising a hydrophilic block and a hydrophobic block.
2 is a schematic view showing a configuration of a general oxidation-flow cell.
3 is ¹ H-NMR of 2,5-dichloro-4'-phenoxybenzophenone (DCPBP) as a hydrophilic monomer.
4 is ¹ H-NMR of 4-chloro-4'-fluorobenzophenone (CFBP).
5 is ¹ H-NMR of trimmer (BCPPF).
6 is ¹ H-NMR of PPA-102 as a block copolymer according to an embodiment of the present invention.
7 is ¹ H-NMR of AMPPA-102, which is an aminated block copolymer according to an embodiment of the present invention.
Figure 8 shows the appearance of the membrane consisting of the aminated block copolymer.
9 shows the ion conductivity of a membrane made of the block copolymer of the present invention in comparison with a conventional membrane.
10 and 11 are the results of evaluating the performance of the membrane made of the block copolymer of the present invention as a separation membrane for an oxidation-flow battery.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples.

Example  1: As the hydrophilic monomer, 2,5- Dichloro -4'- Of phenoxybenzophenone (DCPBP)  synthesis

The inside of the 250 ml flask was filled with Ar atmosphere, and diphenyl ether (28.6 mmol) and dichloromethane were added. An ice bath was installed and aluminum chloride (28.6 mmol) was added. After 30 minutes, 2,5-dichlorobenzoyl chloride (23.9 mmol) was added slowly. After 4 hours, the reaction was terminated and poured into ultra-pure water containing a small amount of HCl. The mixture was extracted with dichloromethane to give the title compound (yield 92%). The compound was confirmed by &lt; ¹ &gt; H-NMR (Fig. 3).

Example  2: Synthesis of hydrophobic monomers

1) Synthesis of 4-chloro-4'-fluorobenzophenone (CFBP)

The inside of the 250 ml flask was filled with Ar atmosphere, and then fluorobenzene (56.1 mmol) and nitromethane were added. An ice bath was installed and aluminum chloride (27.1 mmol) was added. After 30 minutes, p-chlorobenzoyl chloride (28.6 mmol) was added slowly. After 4 hours, the reaction was terminated and poured into ultra-pure water containing a small amount of HCl. The mixture was extracted with dichloromethane to give the title compound (yield 90%). The compound was identified by &lt; ¹ &gt; H-NMR (Fig. 4).

2) Synthesis of trimer (BCPPF)

After filling the inside of the 250 ml flask with the Ar atmosphere, 15.3 g of CFBP, 10 g of 4,4 '- (perfluoropropane-2,2-diyl) diphenol and 65 ml of N, N'-dimethylacetamide were added. After the monomers were all dissolved, potassium carbonate (71.3 mmol) was added. Maintained at 80 ° C for 2 hours, and reacted at 120 ° C for 15 hours. The reaction was terminated and allowed to cool to room temperature. The cooled reaction product was poured into deionized water. The obtained product was recrystallized from toluene (yield: 84%). The compound was confirmed by ¹ H-NMR (FIG. 5).

Example  3: Negative ion conductivity Block copolymer  Synthesis and Fabrication of Polymeric Membrane Using It

1) Synthesis of block copolymer (PPA-102)

Two three-necked flasks were prepared. The inside of the two prepared flasks was changed to Ar atmosphere. To the first flask was added 5 g of BCPPF, 13.1 mmol of DCPBP and 12 ml of N, N'-dimethylacetamide. To the second flask was added nickel bromide (1.4 mmol), triphenylphosphate (9.6 mmol), zinc dust ) (82.3 mmol) and 20 ml of N, N'-dimethylacetamide. The contents of each flask were slowly warmed to 80 &lt; 0 &gt; C. Each flask contents were reacted at 80 DEG C for 1 hour, then the contents of the first flask were poured into the contents of the second flask and reacted at 80 DEG C overnight. After completion of the reaction, the reaction product was precipitated by adding methanol to methanol containing 10 vol% HCl, and the obtained precipitate was washed with methanol. The washed product was dried in a vacuum oven at &lt; RTI ID = 0.0 &gt; 80 C &lt; / RTI & The compound was identified by &lt; ¹ &gt; H-NMR (Fig. 6).

2) Synthesis of chloromethylated PPA-102 (CMPPA-102)

A four-necked flask was prepared and replaced with an Ar atmosphere. 1 g of PPA-102 polymer and 15 ml of 1,1,2,2-tetrachloroethane were added. When the mixture was neatly dissolved, zinc chloride (0.8 mmol) was added thereto and stirred for about 30 minutes. Then, chloromethyl methyl ether (64.24 mmol) was slowly added dropwise and slowly dropped to 40 ° C when the dropping was completed. The reaction was allowed to proceed at 40 占 폚 for 48 hours. The reaction was terminated and washed several times with methanol and then dried in an oven at 80 ° C for one day. The compound was confirmed by &lt; ¹ &gt; H-NMR (Fig. 7).

3) Synthesis / Deposition of Block Copolymer PPA-102 (AMPPA-102) Substituted with Anion Exchanger

0.7 g of CMPPA-102 polymer was dissolved neat in 10 ml of DMAc. The dissolved polymer solution was filtered using a 0.5 탆 syringe filter, and a membrane was formed through mold casting. Specifically, the polymer solution is poured into a silicon mold of a predetermined size and dried at 80 DEG C for 24 hours to obtain a membrane. The resulting membrane was mixed with acetone and a 45 wt% trimethylamine solution at a concentration of 1 M, and the membrane was immersed for 24 hours to quaternize it. The aminated membrane was cleaned with deionized water and then put into a 1M NaOH solution for one day to convert it to OH ^- form.

A film made of the aminated polymer (AMPPA-102) is shown in FIG.

Experimental Example  1: Anion conductivity of the present invention Block copolymer  Ionic conductivity measurement

The ionic conductivity of a film composed of an aminated polymer (AMPPA-102) prepared by the method described in Example 3 above was compared with the ionic conductivity of the compatibilizing film.

AMX of Tokuyama, Japan and VPX of Fumatech (DE) were used as commercial membranes.

Specifically, the ionic conductivity was measured as follows.

The hydroxyl ion conductivities were measured at 25 ° C and 80 ° C at 100% relative humidity using an AC impedance analyzer (Solatron 1280, Impedance / gain phase analyzer). Four prove conductivity cells were measured in the in-phase direction in the range of 0.1 to 20 kHz. The temperature was maintained for 30 minutes in the thermo-hygrostat chamber before measurement, and the conductivity was calculated by the following equation.

Where I is the distance between the electrodes, R is the impedance of the film, and S is the surface area over which the protons move.

The results are shown in Fig.

It can be seen from FIG. 9 that the block copolymer of the present invention exhibits far superior anion conductivity than the commercial membrane.

Experimental Example 2: Oxidation of Membrane Prepared by Anionic Conductive Block Copolymer of the Present Invention [ As a separator  Performance evaluation

A performance evaluation of a film composed of an aminated polymer (AMPPA-102) prepared by the method described in Example 3 above as a separation membrane for an oxidative flow battery was performed as follows.

The VRFB performance test was performed using a WonATech battery test system, and 100 ml of V 3.5 + 1.65 M was used as the electrolytic solution. The electrodes were annealed at 500 ℃ for carbon felt. The cell performance was tested by setting the film size to 100 cm 2, the thickness to 50 μm, the current density to 50 mA / cm 2, and the flow rate to 60 ml / min.

The results are shown in Fig. 10 and Fig.

10 and 11, although the voltage efficiency of the AMPPA-102 was slightly lower than that of the commercially available Nafion 115 membrane, the columbic efficiency was very good and the efficiency was good in terms of energy efficiency.

It has higher columbic efficiency than Nafion and its capacity is also better than AMPPA-102.

Claims (19)

Anionic ion conductors for selective migration of anions comprising anionic conductive polymers represented by the following formula (1)
[Chemical Formula 1]

In this formula,
A is a single bond or an electron withdrawing group which is - (C = O) -, - (P = O) -, -CF ₂ -, - (C (CF ₃ ) ₂ ) - or - (SO ₂ ) -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;
B is -O-, -S-, -NH- or -NR ₂₅ - as a single bond or electron donor group, wherein R ₂₅ is an alkyl group;
Z is an anion exchange functional group, an amphoteric ion exchange functional group or a combination thereof;
W is hydrogen;
a and b are each an integer belonging to 1 to 10;
c is an integer belonging to 1 to 5;
1 is an integer belonging to 1 to 10,000;
D is a single bond or -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group, or

And, wherein G is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - And J is an electron donor group such as -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;
Wherein Ar 'is an unsubstituted or substituted group selected from the group consisting of a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, a cyano group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group; or

And, where P is a bond or an electron withdrawing single group - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - ego;
Ar "refers to an unsubstituted or substituted group containing one or more oxygen, nitrogen or sulfur atoms in the chain, such as a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group;

And, where P 'is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ -ego;
Wherein P and P 'are the same or different from each other;
E is -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group;
R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with at least one halogen, an allyl group, a cyano group, an aryl group, optionally containing at least one oxygen, nitrogen or sulfur atom A perfluoroalkylaryl group, a perfluoroaryl group or an -O-perfluoroaryl group;
q is an integer of 0 or 1;
p is an integer from 1 to 1000;
n is an integer from 1 to 10,000;
X and X 'are each independently a halogen atom.
The method of claim 1, wherein the anion-exchange functional group is _{-NH 3 T, -NR'H 2 T,} -NR '2 HT, -NR' 3 T, -PR '3 T or -SR' ₂ T, or -C ₅ H ₅ NHT and in that (R 'is alkyl or aryl, T is the hydroxide anion, bicarbonate anion, a chloride anion or a sulfate anion Im), an amphoteric ion-exchange functional group is a betaine or alcohol Phoebe other features Anion ion conductor.
The positive electrode of claim 1, wherein E in the anionic conductive polymer is -O-; and p is an integer from 1 to 50.
The anion ion conductor according to claim 1, wherein the anion-conducting polymer is a block copolymer.
The anion-conducting polymer of claim 1, wherein the anion-conducting polymer has a number-average molecular weight (Mn) of 10,000 to 1,000,000 or an average molecular weight (Mw) of 10,000 to 10,000,000. Ion conductor.
The anion ion conductor according to claim 1, which is a molding formed of a resin composition containing the anionic conductive polymer.
The anion ion conductor according to claim 6, wherein the molded body is an electrolyte membrane.
The anion ion conductor according to claim 7, wherein the electrolyte membrane is an electrolyte membrane for an oxidative flow cell, an electrolyte membrane for a fuel cell, an electrolyte membrane for an electrolysis solution, an electrolyte membrane for electrodialysis or an electrolyte membrane for a reverse electrodialysis.
The anion ion conductor according to claim 8, wherein the electrolyte membrane for a fuel cell is applied to a solid alkaline fuel cell or a direct borohydride fuel cell.
The anion ion conductor according to claim 1, wherein the anion conductive polymer is an electrode for a fuel cell including a binder.
The method for producing an anion ion conductor according to any one of claims 1 to 10,
A first step of preparing a hydrophilic monomer represented by the following formula (2);
A second step of preparing a hydrophobic monomer represented by the following formula (3);
A third step of mixing the hydrophilic monomer and the hydrophobic monomer to form a block copolymer by a colon coupling reaction;
A fourth step of halomethylating the block copolymer;
A fifth step of molding the halomethylated block copolymer into a predetermined shape; And
A sixth step of partially or completely replacing the halogen functional group of the formed halomethylated block copolymer with an anion exchangeable functional group, an amphoteric ion-exchange functional group, or a combination thereof;
(2)

(3)

In this formula,
A, B, W, a, b, D, Ar ', Ar ", E, R 1 to R _4, q, p, X and X' are as defined in paragraph 1 above.
12. The method according to claim 11, wherein the third step is performed under a reducing metal and a catalyst.
12. The method according to claim 11, wherein the fourth step is performed by reacting the block copolymer obtained in the third step with halomethyl methyl ether.
An electrolyte membrane comprising the anion ion conductor according to any one of claims 1 to 10.
A fuel cell comprising the anion ion conductor according to any one of claims 1 to 10 in an electrolyte membrane or an electrode.
An oxidized flow cell comprising the anion ion conductor according to any one of claims 1 to 10 in an electrolyte membrane.
A water treatment apparatus comprising the anion ion conductor according to any one of claims 1 to 10 in an electrolyte membrane.
An anionic conductive polymer represented by the following Formula 1:
[Chemical Formula 1]

In this formula,
A is a single bond or an electron withdrawing group which is - (C = O) -, - (P = O) -, -CF ₂ -, - (C (CF ₃ ) ₂ ) - or - (SO ₂ ) -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;
B is -O-, -S-, -NH- or -NR ₂₅ - as a single bond or electron donor group, wherein R ₂₅ is an alkyl group;
Z is an anion exchange functional group, an amphoteric ion exchange functional group or a combination thereof;
W is hydrogen;
a and b are each an integer belonging to 1 to 10;
c is an integer belonging to 1 to 5;
1 is an integer belonging to 1 to 10,000;
D is a single bond or -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group, or

And, wherein G is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - And J is an electron donor group such as -O-, -S-, -NH- or -NR ₂₅ -, wherein R ₂₅ is an alkyl group;
Wherein Ar 'is an unsubstituted or substituted group selected from the group consisting of a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, a cyano group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group; or

And, where P is a bond or an electron withdrawing single group - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ - ego;
Ar "refers to an unsubstituted or substituted group containing one or more oxygen, nitrogen or sulfur atoms in the chain, such as a halogen atom (-X), an alkyl group, an alkyl group substituted with one or more halogens, an allyl group, An aryl group substituted with at least one substituent selected from the group consisting of a perfluoroaryl group, a perfluoroaryl group, and a -O-perfluoroaryl group;

And, where P 'is an electron withdrawing group or a single bond - (C = O) -, - (P = O) -, -CF 2 -, - (C (CF 3) 2) - or - (SO ₂₎ -ego;
Wherein P and P 'are the same or different from each other;
E is -O-, -S-, -NH- or -NR ₂₅ - as an electron donor, wherein R ₂₅ is an alkyl group;
R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with at least one halogen, an allyl group, a cyano group, an aryl group, optionally containing at least one oxygen, nitrogen or sulfur atom A perfluoroalkylaryl group, a perfluoroaryl group or an -O-perfluoroaryl group;
q is an integer of 0 or 1;
p is an integer from 1 to 1000;
n is an integer from 1 to 10,000;
X and X 'are each independently a halogen atom.
A binder composition for an electrode comprising the anionic conductive polymer of claim 18.

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