KR102010399B1 - Compound including aromatic ring, polymer including the same and polymer electrolyte membrane using the same - Google Patents

Abstract

The present specification includes a compound including an aromatic ring, a polymer including the same, a polymer electrolyte membrane including the same, a membrane-electrode assembly including the polymer electrolyte membrane, a fuel cell including the membrane-electrode assembly, and the polymer electrolyte membrane. A redox flow battery.

Description

A compound containing an aromatic ring, a polymer containing the same, and a polymer electrolyte membrane using the same {COMPOUND INCLUDING AROMATIC RING, POLYMER INCLUDING THE SAME AND POLYMER ELECTROLYTE MEMBRANE USING THE SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2016-0018432 filed with the Korea Patent Office on February 17, 2016, the entire contents of which are incorporated herein.

The present specification relates to a compound including an aromatic ring, a polymer including the same, and a polymer electrolyte membrane using the same.

A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy. In other words, a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the oxidation / reduction reaction. The membrane electrode assembly (MEA) of a fuel cell is a portion in which an electrochemical reaction between hydrogen and oxygen occurs and is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane.

A redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy by charging and discharging the active material contained in the electrolyte. to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).

Fuel cells and redox flow cells are being researched and developed as next generation energy sources due to their high energy efficiency and eco-friendly features with low emissions.

The key components of fuel cell and redox flow cell are polymer electrolyte membranes capable of cation exchange, including 1) excellent proton conductivity 2) prevention of crossover of electrolyte, 3) strong chemical resistance, 4) mechanical It is desirable to have properties of enhanced physical properties and / or 5) low swelling ratio. The polymer electrolyte membrane is classified into fluorine-based, partially fluorine-based, hydrocarbon-based, and the like, and the partial fluorine-based polymer electrolyte membrane has a fluorine-based main chain, which has advantages of excellent physical and chemical stability and high thermal stability. In addition, as in the fluorine-based polymer electrolyte membrane, the partial fluorine-based polymer electrolyte membrane has a cation transfer functional group attached to the end of the fluorine-based chain, and thus has the advantages of a hydrocarbon-based polymer electrolyte membrane and a fluorine-based polymer electrolyte membrane.

In the case of a fuel cell and / or a redox flow battery, there are various advantages such as improving the reactivity of the anode and reducing water film phenomenon and catalyst contamination when operating at low humidity conditions. However, in the case of polymer electrolyte membranes which are generally used, there is a problem in that physical properties such as cation conductivity are decreased in low-humidity conditions, resulting in a sudden decrease in battery performance. Therefore, research is needed to solve this problem.

Republic of Korea Publication No. 2003-0076057

The present specification is to provide a compound containing an aromatic ring and a polymer electrolyte membrane using the same.

According to an exemplary embodiment of the present specification, a compound including an aromatic ring represented by the following formula (1) is provided.

[Formula 1]

In Chemical Formula 1,

R1 and R3 to R5 are the same as or different from each other, and each independently hydrogen, a hydroxy group or a halogen group,

R6 is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - is selected from the group consisting of M ⁺ and -PO ₃ ^2- 2M ⁺ ,

또는

이고, R 2 is O, S, NH, SO ₂ ,

or

ego,

L 1 is a direct bond; Or O,

n is an integer from 1 to 10, and the structures in 2 to 10 parentheses are the same as or different from each other,

M is a group 1 element.

An exemplary embodiment of the present specification provides a polymer including a monomer derived from the compound of Formula 1.

The present specification provides a polymer electrolyte membrane including a polymer including a monomer derived from the compound of Formula 1 above.

In addition, an exemplary embodiment of the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.

In addition, an exemplary embodiment of the present disclosure is two or more of the aforementioned membrane-electrode assembly; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.

In addition, an exemplary embodiment of the present specification includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising the above-described polymer electrolyte membrane provided between the cathode cell and the anode cell.

A polymer electrolyte membrane prepared using a polymer including a monomer derived from a compound according to one embodiment of the present specification has excellent ion conductivity.

In addition, the polymer electrolyte membrane prepared by using a polymer including a monomer derived from a compound according to one embodiment of the present specification has a high ion exchange capacity (IEC) value under high humidity and / or low humidity conditions. .

In addition, the polymer containing a monomer derived from a compound according to an embodiment of the present disclosure has a low acid dissociation constant (pK _a ) because it has a multi acid including at least two acid units per unit structure. Rather, it is easy to phase-separate the polymer electrolyte membrane using this, and consequently, the ionic conductivity is improved.

In addition, the fuel cell and / or the redox flow battery including the polymer electrolyte membrane have excellent durability and efficiency.

1 is a schematic diagram illustrating a principle of electricity generation of a fuel cell.
2 is a view schematically showing a general structure of a redox flow battery.
3 is a view schematically showing an embodiment of a fuel cell.
4 is a graph showing the H-NMR value of the compound 6 according to an exemplary embodiment of the present specification.
5 is a graph showing F-NMR values of the compounds 5 and 6 according to an exemplary embodiment of the present specification.
6 is a graph showing the FT-IR value of Polymer 1 according to an exemplary embodiment of the present specification.
7 is a graph showing a molecular weight value measured by GPC for Polymer 1 according to an exemplary embodiment of the present specification.

Hereinafter, the present specification will be described in more detail.

In general, the polymer electrolyte membrane used has excellent efficiency in a high humidification state, but has a problem of low cation conductivity in low humidity conditions. However, in the present specification, the problem may be improved by using the compound represented by Chemical Formula 1 described above.

Specifically, in the present specification, the compound including the aromatic ring represented by Formula 1 includes two benzene rings each containing disulfonamide (disulfonamide, -SO ₂ NHSO _2- ), which may act as a multi acid, Linkers to link and acids at the ends. The acid is an ion transfer functional group, -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ and -PO ₃ ^{2 -} is selected from the group consisting of 2M ^+. Therefore, the polymer including the monomer derived from the compound represented by Formula 1 increases the number of acids per unit unit, and the ion exchange capacity (IEC) value of the polymer electrolyte membrane including the polymer increases. Can be. As a result, the polymer electrolyte membrane may exhibit excellent cation conductivity even under high humidity conditions as well as low humidity conditions.

According to an exemplary embodiment of the present specification, in the general formula 1, at least one of R1 and R3 to R5 is a halogen group, the remainder is hydrogen, the halogen group is fluorine (F) or chlorine (Cl).

According to an exemplary embodiment of the present specification, in the general formula 1, R5 is fluorine (F), R1, R3 and R4 are hydrogen.

According to an exemplary embodiment of the present specification, in the general formula 1, R2 is SO ₂ .

According to an exemplary embodiment of the present specification, in the general formula 1, L1 is a direct bond.

According to an exemplary embodiment of the present specification, in the general formula 1, L1 is O.

According to an exemplary embodiment of the present specification, in the general formula 1, wherein R6 is -SO ₃ H or -SO ₃ ^- M ⁺ .

According to an exemplary embodiment of the present specification, the group 1 element M may be Li, Na or K.

According to an exemplary embodiment of the present specification, in the general formula 1, wherein R6 is -SO ₃ H.

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 is any one selected from the following structures.

An exemplary embodiment of the present specification provides a polymer including a monomer derived from the compound represented by Chemical Formula 1. As described above, the monomer has an advantage of showing improved reactivity during the polymerization reaction.

In the present specification, "monomer" means a structure in which the compound is included in the form of two or more in the polymer by the polymerization reaction. Specifically, the monomer derived from the compound represented by Formula 1 may have a structure as shown in Formula 2. However, the present invention is not limited thereto.

[Formula 2]

In Formula 2, the definitions of R 2, R 6, L 1, and n are the same as those of Formula 1.

The polymer according to the exemplary embodiment of the present specification includes a monomer derived from the compound represented by Chemical Formula 1 as described above. Because of this, since the ion-transfer functional group including the partial fluorine-based in the polymer is present in the pendant (pendant) form, the ion-transfer functional groups in the polymer easily gather together to facilitate phase separation to easily form an ion channel, and consequently form the polymer It is possible to implement the effect of improving the ion conductivity of the polymer electrolyte membrane comprising. In addition, since it contains a multi acid containing two acid units (acid units) per monomer unit structure, the effect of improving the ion conductivity is more excellent.

According to an exemplary embodiment of the present specification, the polymer may be a random polymer. In this case, a polymer having a high molecular weight can be obtained by a simple polymerization method.

At this time, the monomer derived from the compound represented by Formula 1 serves to control the ionic conductivity of the polymer electrolyte membrane including the polymer, the remaining proportion of the comonomer polymerized in a random form serves to improve the mechanical strength do.

According to an exemplary embodiment of the present specification, the monomer derived from the compound represented by Formula 1 may be included in 0.1 mol% to 100 mol% of the entire polymer. Specifically, the polymer includes only monomers derived from the compound represented by Chemical Formula 1. In another exemplary embodiment, the polymer may further include a second monomer other than the monomer derived from the compound represented by Chemical Formula 1. In this case, the content of the monomer derived from the compound represented by the formula (1) is preferably 0.5 mol% to 65 mol%. More preferably, it may be 5 mol% to 65 mol%. Polymers comprising monomers derived from compounds within this range have mechanical strength and high ionic conductivity.

As the second monomer, those known in the art may be used. In this case, one kind or two or more kinds of the second monomer may be used.

Examples of the second monomer include perfluorosulfonic acid polymer, hydrocarbon-based polymer, polyimide, polyvinylidene fluoride, polyether sulfone, polyphenylene sulfide, polyphenylene oxide, polyphosphazine, polyethylene naphthalate, polyester, Doped polybenzimidazoles, polyetherketones, polysulfones, monomers thereof or bases thereof may be used.

According to an exemplary embodiment of the present invention, the polymer may include a repeating unit represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

A is represented by Formula 2,

B includes a unit derived from formula (4)

C includes a unit derived from formula (5)

u: v is from 1: 100 to 100: 1,

[Formula 4]

In Chemical Formula 4,

X is a direct bond or -C (Z1) (Z2)-; —CO—; —O—; -S-; —SO ₂ —; And -Si (Z1) (Z2)-, and

[Formula 5]

In Chemical Formula 5,

Y is a direct bond or -C (Z1) (Z2)-; —CO—; —O—; -S-; —SO ₂ —; And -Si (Z1) (Z2)-, and

Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present specification, Chemical Formula 4 may be represented by any one selected from the following structural formulas.

According to an exemplary embodiment of the present specification, X is a direct bond.

According to an exemplary embodiment of the present specification, Chemical Formula 5 may be represented by any one selected from the following structural formulas.

According to an exemplary embodiment of the present disclosure, wherein Y is -SO _2- .

According to one embodiment of the present specification, the content of the second monomer in the polymer may be greater than 0 wt% and 99.9 wt% or less.

According to the exemplary embodiment of the present specification, in the repeating unit represented by Formula 3, the molar ratio of A may be 0.1 to 0.5, the molar ratio of B may be 0.5 to 2.0, and the molar ratio of C may be 0.5 to 1.0. More preferably, the molar ratio of A is 0.1 to 0.3, the molar ratio of B is 0.8 to 1.2, and the molar ratio of C may be 0.7 to 0.9.

According to an exemplary embodiment of the present specification, when the polymer includes the second monomer, the polymer may be a random polymer.

An exemplary embodiment of the present specification also provides a polymer electrolyte membrane including the polymer. The polymer electrolyte membrane may exhibit the above effects.

In the present specification, "electrolyte membrane" is a membrane capable of exchanging ions, such as membrane, ion exchange membrane, ion transfer membrane, ion conductive membrane, separator, ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion And a transfer electrolyte membrane or an ion conductive electrolyte membrane.

The polymer electrolyte membrane according to the present specification may be manufactured using materials and / or methods known in the art, except for including monomers derived from the compound represented by Chemical Formula 1.

According to another exemplary embodiment, the weight average molecular weight of the polymer included in the polymer electrolyte membrane may be 500 or more and 5,000,000 or less (g / mol), specifically 20,000 or more and 2,000,000 or less (g / mol), More specifically, it may be 50,000 or more and 1,000,000 or less (g / mol).

When the weight average molecular weight of the copolymer is 500 or more and 5,000,000 or less (g / mol), the mechanical properties of the electrolyte membrane are not lowered, so that the preparation of the electrolyte membrane can be facilitated by maintaining appropriate solubility of the polymer.

According to an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g. When the ion exchange capacity is in the range, an ion channel in the polymer electrolyte membrane is formed, and the polymer may exhibit ion conductivity.

According to one embodiment of the present specification, the thickness of the electrolyte membrane may be 1 μm to 500 μm, and specifically 10 μm to 200 μm. When the thickness of the electrolyte membrane is 1 μm to 500 μm, electric short and crossover of the electrolyte material may be reduced, and excellent cation conductivity may be exhibited.

According to an exemplary embodiment of the present specification, the ionic conductivity of the polymer electrolyte membrane may be 0.001 S / cm or more and 0.5 S / cm or less, specifically, may be 0.01 S / cm or more and 0.5 S / cm or less.

According to another exemplary embodiment, the ionic conductivity of the polymer electrolyte membrane may be measured under humidification conditions. The humidification condition may mean full humidification condition, may mean 10% to 100% relative humidity (RH), or may mean 30% to 100% relative humidity (RH).

According to one embodiment of the present specification, the ionic conductivity of the polymer electrolyte membrane may be 0.001 S / cm or more and 0.5 S / cm or less, and may be measured at 10% to 100% relative humidity (RH). According to another exemplary embodiment, the ionic conductivity of the polymer electrolyte membrane may be 0.01 S / cm or more and 0.5 S / cm or less, and may be measured at a relative humidity (RH) of 30% to 100%.

According to an exemplary embodiment of the present specification, at least some of the polymer may be in the form of a metal salt. In addition, the metal salt may be substituted in the form of an acid.

Specifically, R6 is -SO ₃ in the formula ^{1 - M +, -COO - M} +, -PO 3 H - M +, or -PO ₃ ^2- 2M ⁺ is a metal added to the acid solution in place of Polymer M H ( An electrolyte membrane including a polymer substituted with hydrogen) may be formed.

According to one embodiment of the present specification, it may be a general acid solution used for the acid treatment, specifically, may be hydrochloric acid or sulfuric acid.

According to an exemplary embodiment of the present specification, the concentration of the acid solution may be 0.1M or more and 10M or less, specifically 1M or more and 2M or less. When the concentration of the acid solution is 0.1M or more and 10M or less, it can be easily replaced with hydrogen instead of metal M without damaging the electrolyte membrane.

One embodiment of the present specification also includes an anode; Cathode; It provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.

Membrane-electrode assembly (MEA) is an electrode (cathode and anode) in which the electrochemical catalysis of fuel and air occurs and a polymer membrane in which hydrogen ions are transferred. The electrode (cathode and anode) and the electrolyte membrane are bonded together. It is a single unitary unit.

The membrane-electrode assembly of the present specification is a form in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane, and may be prepared according to conventional methods known in the art. In one example, the cathode; Anode; And it may be prepared by thermal compression to 100 to 400 in a state in which the electrolyte membrane located between the cathode and the anode in close contact.

The anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may again include an anode microporous layer and an anode electrode substrate.

The cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may further include a cathode microporous layer and a cathode electrode substrate.

FIG. 1 schematically illustrates the principle of electricity generation of a fuel cell. In the fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is an electrolyte membrane 100 and the electrolyte membrane 100. It consists of an anode (200a) and a cathode (200b) electrode formed on both sides of the. Referring to FIG. 1, which illustrates a principle of electricity generation of a fuel cell, an anode 200a generates an oxidation reaction of a fuel such as hydrogen or a hydrocarbon such as methanol and butane to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ). The hydrogen ions move to the cathode 200b through the electrolyte membrane 100. In the cathode 200b, water is generated by reacting hydrogen ions transferred through the electrolyte membrane 100 with an oxidant such as oxygen and electrons. This reaction causes the movement of electrons in the external circuit.

The catalyst layer of the anode electrode is where the oxidation reaction of the fuel occurs, the catalyst is selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-transition metal alloy. Can be used. The catalyst layer of the cathode electrode is where the reduction reaction of the oxidant occurs, platinum or platinum-transition metal alloy may be preferably used as a catalyst. The catalysts can be used on their own as well as supported on a carbon-based carrier.

The introduction of the catalyst layer may be carried out by conventional methods known in the art, for example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. At this time, the coating method of the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used. Catalytic inks can typically consist of a catalyst, a polymer ionomer, and a solvent.

The gas diffusion layer serves as a passage for the reaction gas and water together with a role as a current conductor, and has a porous structure. Therefore, the gas diffusion layer may include a conductive substrate. As the conductive substrate, carbon paper, carbon cloth or carbon felt may be preferably used. The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive substrate. The microporous layer may be used to improve the performance of the fuel cell in low-humidity conditions, and serves to reduce the amount of water flowing out of the gas diffusion layer so that the electrolyte membrane is in a sufficient wet state.

One embodiment of the present specification includes two or more of the aforementioned membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.

When the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a fuel cell, the above-described effects can be obtained.

A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy. In other words, a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.

The fuel cell can be manufactured according to conventional methods known in the art using the membrane-electrode assembly (MEA) described above. For example, it may be prepared by configuring a membrane-electrode assembly (MEA) and a bipolar plate prepared above.

The fuel cell of the present specification includes a stack, a fuel supply unit and an oxidant supply unit.

3 schematically illustrates the structure of a fuel cell, in which the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.

The stack 60 includes one or two or more membrane electrode assemblies as described above, and includes two or more separators interposed therebetween when two or more membrane electrode assemblies are included. The separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidant supply unit 70 serves to supply the oxidant to the stack 60. Oxygen is typically used as the oxidant, and may be used by injecting oxygen or air into the oxidant supply unit 70.

The fuel supply unit 80 serves to supply fuel to the stack 60, and to the fuel tank 81 storing fuel and the pump 82 supplying fuel stored in the fuel tank 81 to the stack 60. Can be configured. As fuel, hydrogen or hydrocarbon fuel in gas or liquid state may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The fuel cell may be a polymer electrolyte fuel cell, a direct liquid fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, a direct ethanol fuel cell, or a direct dimethyl ether fuel cell.

In addition, an exemplary embodiment of the present specification includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising a polymer electrolyte membrane according to one embodiment of the present specification provided between the cathode cell and the anode cell.

The redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy. It is a system in which the active material contained in the electrolyte is oxidized, reduced, and charged and discharged. to be. The redox flow battery uses a principle that charges and discharges are exchanged when electrons containing active materials having different oxidation states meet with an ion exchange membrane interposed therebetween. In general, a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte solution between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, an electrolyte, and an ion. Exchange membrane.

When the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a redox flow battery, the above-described effects may be exhibited.

The redox flow battery of the present specification may be manufactured according to conventional methods known in the art, except for including the polymer electrolyte membrane according to one embodiment of the present specification.

As shown in FIG. 2, the redox flow battery is divided into the positive electrode cell 32 and the negative electrode cell 33 by the electrolyte membrane 31. The anode cell 32 and the cathode cell 33 include an anode and a cathode, respectively. The anode cell 32 is connected to the anode tank 10 for supplying and discharging the anode electrolyte 41 through a pipe. The cathode cell 33 is also connected to the cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe. The electrolyte is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions changes occurs, so that charging and discharging occur at the positive electrode and the negative electrode.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

<Manufacture example 1>

1) Synthesis of Compound 3

10 g (30.65 mmol) of Compound 1 (Sodium 5,5′-sulfonylbis (2-fluorobenzenesulfonate)) was dissolved in 100 ml of POCl ₃ , and then 15.32 g (73.57 mmol) of PCl ₅ was added thereto and heated to 120 ° C. The reaction was stirred at 120 ° C. for 1 hour and then warmed again, stirred at 150 ° C. for 2 hours and cooled to room temperature. The reaction was distilled under reduced pressure under high pressure to remove excess POCl ₃ , dissolved in CH ₂ Cl ₂ and washed several times with water at 0 ° C. The organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain a crude sulfonyl chloride compound. Sulfonyl chloride compounds were dissolved in CH ₂ Cl ₂ without further purification, cooled to 0 ° C., and 100 ml of ammonia water was slowly added dropwise. After slowly raising the temperature and reacting at room temperature for 16 hours, the mixture was distilled under reduced pressure under high pressure. The obtained compound was dissolved in ethyl acetate and washed several times with water. The organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain 4.58 g of Compound 3 (5,5'-sulfonylbis (2-fluorobenzenesulfonamide)) (yield 45.9%). )

2) Synthesis of Compound 5

4.58 g (14.1 mmol) of Compound 3 (5,5'-sulfonylbis (2-fluorobenzenesulfonamide)) obtained above was dissolved in 40 ml of acetonitrile, and then Compound 4 (1,1,2,2-tetrafluoroethane-1,2- disulfonyl dichloride) 8.52 g (31 mmol) was added and the reaction was cooled to 0 ° C. 11.3ml (84 mmol) of Et ₃ N was slowly added dropwise to the reaction at 0 ° C, and the temperature was gradually raised to room temperature and stirred for about 1 to 2 hours. The crude compound obtained by distillation under reduced pressure was dissolved in ethyl acetate, and then washed several times with 1N HCl to remove Et ₃ N. The organic layer was separated, dried over MgSO ₄ , distilled, and then purified by column chromatography using methylene chloride: methyl alcohol = 9: 1 to obtain Compound 5 (2,2 '-(5,5'-sulfonylbis ( 6.75 g (yield 85%) of 2-fluoro-5,1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethanesulfonyl chloride)) were obtained.

3) Synthesis of Compound 6

6.75 g (12.0 mmol) of Compound 5 (2,2 '-(5,5'-sulfonylbis (2-fluoro-5,1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethanesulfonyl chloride)) obtained above After dissolving in 40 ml of 1,4-Dioxane, 40 ml of 10% HCl was added and heated to 100 ° C. The reaction was stirred at 100 ° C. for 16 hours, then cooled to room temperature and all solvents were removed by distillation under reduced pressure. The obtained crude compound was dissolved in H ₂ O, washed several times with CH ₂ Cl ₂ to remove impurities, and the remaining water layer was distilled under reduced pressure. The solid compound obtained by dissolving the compound in CH ₂ Cl ₂ and slowly dropwise addition to n-Hexane was filtered and dried under N ₂ gas to dry the compound 6 (2,2 '-(sulfonylbis (6-fluoro-3). , 1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethane-1-sulfonic acid)) 5.62 g (yield 86.0%) was obtained.

4 is a graph showing the H-NMR value of the compound 6 synthesized in Preparation Example 1. FIG.

5 is a graph showing F-NMR values of the compounds 5 and 6 synthesized in Preparation Example 1. FIG.

Preparation Example 2 Synthesis of Random Polymer 1

Each monomer and potassium carbonate (molar ratio 0.2: 1.0: 0.8, K ₂ CO ₃ : molar ratio 4) were mixed at a ratio of 20 wt% of dimethyl sulfoxide (DMSO) and 20 wt% of benzene, and 180 ° C at 140 ° C for 4 hours. The polymer 1 was prepared by polymerization at 16 ° C. for 16 hours.

6 is a graph showing the FT-IR value of the polymer 1 synthesized in Preparation Example 2. FIG.

Table 1 below shows the molecular weight values measured by GPC for Polymer 1 synthesized in Production Example 2.

Mn Mw MP (Daltons) PDI % Area 5.96 x 10 ⁴ 1.24 X 10 ⁵ 7.97 X 10 ⁴ 2.08 100.00

7 is a graph showing molecular weight values measured by GPC of Polymer 1 synthesized in Preparation Example 2. FIG.

< Production Example  3> Synthesis of Random Polymer 2

Each monomer and potassium carbonate (molar ratio 0.2: 1.0: 0.8, K ₂ CO ₃ : molar ratio 4) were mixed at a ratio of 20 wt% of dimethyl sulfoxide (DMSO) and 20 wt% of benzene, and 180 ° C at 140 ° C for 4 hours. The polymer 2 was prepared by polymerization at 16 ° C. for 16 hours.

<Example 1>

The polymer electrolyte membrane was prepared using the polymer 1 obtained in Preparation Example 2, the molecular weight was measured through GPC, and the results of measuring the cation conductivity and ion exchange capacity (IEC) of the pure membrane are shown in Table 2 below.

Comparative Example 1

The polymer electrolyte membrane was prepared using the polymer 2 obtained in Preparation Example 3, the molecular weight was measured through GPC, and the result of measuring the cation conductivity and ion exchange capacity (IEC) of the pure membrane is shown in Table 2 below.

Mn
(g / mol) Mw
(g / mol) PDI
(Mw / Mn) Ionic Conductivity (S / cm) Ion exchange capacity
IEC (mmol / g) Example 1 59,600 124,000 2.08 0.126 2.16 Comparative Example 1 62,000 486,000 7.8 0.11 1.91

When a polymer containing a monomer derived from a compound containing an aromatic ring represented by Formula 1 according to Example 1 was used as the polymer electrolyte membrane, at least two acid units per unit structure compared to the pure membrane of Comparative Example 1 Because of the multi acid containing unit), it was confirmed that the phase separation is easy, and as a result, the ion conductivity is improved, and the ion exchange capacity (IEC) value is high under high humidity and / or low humidity conditions.

100: electrolyte membrane
200a: anode
200b: cathode
10, 20: tank
11, 21: pump
31: electrolyte membrane
32: anode cell
33: cathode cell
41: anode electrolyte
42: cathodic electrolyte
60: stack
70: oxidant supply
80: fuel supply
81: fuel tank
82: pump

Claims (15)

A compound containing an aromatic ring represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R1 and R3 to R5 are the same as or different from each other, and each independently hydrogen or a halogen group,
R6 is -SO ₃ H or -SO ₃ ^- M ⁺ ,
R ₂ is SO ₂ ,
L1 is a direct bond,
n is 1,
M is a group 1 element. delete delete The compound of claim 1, wherein the compound including the aromatic ring represented by Chemical Formula 1 has the following structure:

A polymer comprising a monomer derived from the compound of claim 1, wherein the monomer has a structure of formula (II):
[Formula 2]

In Formula 2, the definitions of R 2, R 6, L 1, and n are the same as those of Formula 1. delete The polymer of claim 5 wherein the polymer is a random polymer. The polymer of claim 5, wherein the polymer has a weight average molecular weight of 500 g / mol to 5,000,000 g / mol. A polymer electrolyte membrane comprising the polymer of any one of claims 5, 7 and 8. The method according to claim 9,
The ion conductivity of the polymer electrolyte membrane is 0.001 S / cm to 0.5 S / cm polymer electrolyte membrane. The method according to claim 9,
The ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g polymer electrolyte membrane. The method according to claim 9,
The polymer electrolyte membrane has a thickness of 1 μm to 500 μm. Anode; Cathode; And a polymer electrolyte membrane of claim 9 provided between the anode and the cathode. Two or more membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack, wherein the membrane-electrode assembly comprises: an anode; Cathode; And a polymer electrolyte membrane provided between the anode and the cathode, wherein the polymer electrolyte membrane comprises the polymer of any one of claims 5, 7 and 8. A cathode cell comprising an anode and an anode electrolyte solution; A cathode cell comprising a cathode and a cathode electrolyte; And a polymer electrolyte membrane provided between the cathode cell and the anode cell, wherein the polymer electrolyte membrane comprises the polymer of any one of claims 5, 7, and 8.

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