KR102050626B1 - Polymer and polymer electrolyte membrane using the same - Google Patents

Abstract

The present specification relates to a polymer having improved ion transfer ability, 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 a redox flow battery including the polymer electrolyte membrane. will be.

Description

POLYMER AND POLYMER ELECTROLYTE MEMBRANE USING THE SAME

The present specification relates to a polymer and a polymer electrolyte membrane including 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 redox 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, and 4) mechanical properties. And / or 4) 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.

However, the partial fluorine-based polymer electrolyte membrane has a problem that the cation conductivity is relatively low because the fine phase separation of the cation transport functional group and the control of the aggregation phenomenon are not effectively performed. Therefore, research has been conducted toward securing high cationic conductivity through the control of the distribution of sulfonic acid groups and microphase separation.

Korean Unexamined Patent Publication No. 10-2003-0076057

The present specification is to provide a polymer with improved ion transfer capacity and a polymer electrolyte membrane comprising the same.

Herein is a first monomer represented by the formula (1); And

Provided are polymers different from the first monomer and comprising a second monomer having at least one sulfonic acid group.

[Formula 1]

In Chemical Formula 1,

A is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , -PO ₃ ^2- 2M ⁺ , —O (CF ₂ ) _m SO ₃ H, —O (CF ₂ ) _m SO ₃ ^- M ⁺ , —O (CF ₂ ) _m COOH, —O (CF ₂ ) _m COO ^- M ⁺ , —O (CF _{2 ) m PO 3 H 2, -O} (CF 2) m PO 3 H - m + , or -O (CF _{2) m} PO ₃ and ^2- 2M ^+,

m is an integer from 1 to 6,

M is a group 1 element,

R1 and R2 are the same as or different from each other, and each independently a halogen group,

n is an integer from 1 to 10,

When m and n are two or more, the structures in two or more parentheses are the same or different from each other.

In addition, the present disclosure provides a polymer electrolyte membrane including the polymer.

In addition, the present specification; And it provides a reinforcing film comprising the polymer.

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, the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described reinforcement film provided between the anode and the cathode.

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.

In addition, the present specification is a positive electrode cell comprising 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.

Finally, the present specification is a positive electrode cell comprising 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 reinforcement film provided between the positive electrode cell and the negative electrode cell.

The polymer electrolyte membrane including the polymer according to one embodiment of the present specification is advantageous for forming a hydrophilic channel.

In addition, the polymer electrolyte membrane effectively forms a hydrophilic channel in the polymer electrolyte membrane by controlling the phase separation structure.

In addition, the polymer electrolyte membrane has excellent proton conductivity. The result is a high performance of fuel cells and / or redox flow cells comprising the same.

1 is a schematic diagram illustrating a principle of electricity generation of a fuel cell.
2 is a view schematically showing an embodiment of a redox flow battery.
3 is a view schematically showing an embodiment of a fuel cell.
4 is a graph showing a GC mass spectrometry graph of an ion exchange membrane to which the polymer of Example 1 is applied.
5 is a graph showing a GC mass spectrometry graph of an ion exchange membrane to which the polymer of Comparative Example 1 is applied.

Hereinafter, this specification is demonstrated in detail.

In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.

In one embodiment of the present specification, the first monomer represented by Formula 1; And a second monomer different from the first monomer and having at least one sulfonic acid group.

In the present specification, an O atom is used as a linker of the-[CR1R2] _n- A structure and the benzene ring in the general formula (1). In this case, due to the electron withdrawing character of-[CR1R2] _n -A connected by O atoms, it is possible to provide a polymer that is easy to form a polymer and stable.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a halogen group. Specifically, R1 and R2 are each independently F; Cl; Br; And I can be selected from the group consisting of.

When the polymer including the first monomer represented by Chemical Formula 1 of the present specification is included in the polymer electrolyte membrane, when R1 and R2 of Chemical Formula 1 are halogen groups, electrons are well attracted to increase the acidity of the A functional group at the terminal to increase hydrogen. It is possible to facilitate the movement of ions, there is an advantage that can strengthen the structure of the polymer electrolyte membrane. Specifically, according to one embodiment of the present specification, when R1 and R2 are fluorine, the advantages can be maximized.

According to an exemplary embodiment of the present specification, R1 and R2 substituted in the carbon adjacent to A in Formula 1 may serve to increase decationicization.

In one embodiment of the present specification, by including a second monomer different from the first monomer and having at least one sulfonic acid group, the maximum ion exchange capacity (IEC) of the polymer may be increased, and You can expect an increase. Therefore, it is advantageous to form a hydrophilic channel of a polymer electrolyte membrane including a polymer according to one embodiment of the present specification.

In one embodiment of the present specification, n is an integer of 2 to 10. In another embodiment of the present specification, n is an integer of 2 to 6.

The monomer represented by Formula 1 according to an exemplary embodiment of the present specification may adjust the number of n. In this case, by controlling the length of the structure in the parentheses, it may serve to facilitate the phase separation phenomenon of the polymer electrolyte membrane, it is possible to facilitate the movement of hydrogen ions in the polymer electrolyte membrane.

In one embodiment of the present specification, n is 2.

In another embodiment, n is 3.

In another embodiment, n is 4.

In another embodiment, n is 5.

In another exemplary embodiment, n is 6.

In another embodiment, n is 7.

In one embodiment of the present specification, n is 8.

In another embodiment, n is 9.

In one embodiment of the present specification, n is 10.

In one embodiment of the present specification, A is -SO ₃ H or -SO ₃ ^- M ⁺ .

In another embodiment, A is —SO ₃ H.

As described above, is any of formulas A 1 -SO ₃ H or -SO ₃ ^- M ⁺ may be the case, form a stable polymer chemically.

In one embodiment of the present specification, M is a Group 1 element.

In the present specification, the Group 1 element may be Li, Na, or K.

In one embodiment of the present specification, the monomer represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-9.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In one embodiment of the present specification, the second monomer is derived from a compound represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

A1 to A4 are the same as or different from each other, and each independently a hydroxyl group; Or a halogen group,

L 1 is a direct bond; CR3R4; C = O; O; S; SO ₂ ; SiR5R6; Or a substituted or unsubstituted fluorenylene group,

R3 to R6 are the same as or different from each other, and each independently hydrogen; An alkyl group; Fluorine; Haloalkyl group; Or a phenyl group,

S1 to S3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Haloalkyl group; Sulfonic acid groups; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

s1, s2 and s3 are each an integer of 1 to 4,

m 'is an integer from 1 to 5,

When s1, s2, s3 and m 'are integers of 2 or more, the structures in the two or more parentheses are the same or different from each other,

Formula 2 and Formula 3 are substituted with at least one sulfonic acid group.

In one embodiment of the present specification, A1 is a hydroxy group.

In another exemplary embodiment, A1 is a halogen group.

In one embodiment of the present specification, A2 is a hydroxy group.

In another embodiment, A2 is a halogen group.

In one embodiment of the present specification, L1 is SO ₂ .

In one embodiment of the present specification, the second monomer is derived from a compound represented by any one of Formulas 2-1 to 2-4, 3-1, and 3-2.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 3-1]

[Formula 3-2]

In Chemical Formulas 2-2, 2-4 and 3-2,

A1 'and A2' are the same as or different from each other, and are each independently a halogen group.

In one embodiment of the present specification, the second monomer may be selected from the following structures.

In the present specification, the halogen group is fluorine; Goat; bromine; Or iodine.

As used herein, the term "derived" means that a bond is broken or a new bond is generated while a substituent is separated, and the monomer derived from the compound may mean a repeating unit constituting the polymer. The monomer may be included in the main chain in the polymer to constitute the polymer.

Specifically, hydrogen may be separated from the hydroxy group (-OH) substituted with Formulas 2 and 3 or may be included in the polymer while the halogen group is separated to form a repeating unit, that is, a monomer.

In one embodiment of the present specification, the polymer may further include a brancher. In the present specification, a brancher serves to link or crosslink a polymer chain.

In the present specification, in the case of the polymer further including the brancher, the brancher may directly constitute the main chain of the polymer, and may improve the mechanical density of the thin film. For example, the branched polymers of the present invention can be post-treated sulfonated by polymerizing branched hydrophobic blocks that do not contain acid substituents and branched hydrophilic blocks that include acid substituents. Without the post-sulfonation or cross-linking of the sulfonated polymer, the brancher directly forms the main chain of the polymer and maintains the mechanical density of the thin film. Minority blocks and hydrophilic blocks that impart ionic conductivity to the thin film may alternately lead to chemical bonding.

In one embodiment of the present specification, the polymer further includes a brancher derived from a compound of Formula 4 or a brancher represented by Formula 5 below.

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,

X is S; O; CO; SO; SO ₂ ; NR; Hydrocarbon-based or fluorine-based conjugates,

l is an integer from 0 to 100,

when l is 2 or more, two or more X are the same as or different from each other,

Y1 and Y2 are the same as or different from each other, and each independently NRR; An aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,

R is an aromatic ring substituted with a halogen group; Or an aliphatic ring substituted with a halogen group,

Z is a trivalent organic group.

Examples of the substituents herein are described below, but are not limited thereto.

는 인접한 치환기 또는 중합체의 주쇄와 결합함을 의미한다.In the present specification,

Means bonding with the backbone of an adjacent substituent or polymer.

In the present specification, a brancher derived from the compound of Formula 4 may include an aromatic ring substituted with a halogen group of each of Y1 and Y2; Or a halogen group in the aliphatic ring substituted with a halogen group may act as a brancher while being separated from the aromatic ring or aliphatic ring.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

In the present specification, the hydrocarbon-based means an organic compound consisting of only carbon and hydrogen, and includes a straight chain, branched chain, cyclic hydrocarbon, and the like, but is not limited thereto. In addition, it may include a single bond, a double bond or a triple bond, but is not limited thereto.

In the present specification, the fluorine-based conjugate means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.

In the present specification, the aromatic ring may be an aromatic hydrocarbon ring or an aromatic hetero ring, and may be monocyclic or polycyclic.

Specifically, examples of the aromatic hydrocarbon ring include monocyclic aromatics such as phenyl group, biphenyl group and terphenyl group, and naphthyl group, vinaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, peryllenyl group, tetrasenyl group and chrysenyl group. And polycyclic aromatics such as fluorenyl group, acenaphthasenyl group, triphenylene group, and fluoranthene group, and the like.

In the present specification, the aromatic heterocycle means a structure including one or more hetero atoms such as O, S, N, Se, or the like instead of a carbon atom in the aromatic hydrocarbon ring. Specifically, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group , Oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic hetero ring, and may be monocyclic or polycyclic. Examples of the aliphatic ring include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.

In this specification, an organic group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned. This organic group may contain the bond and substituents other than hydrocarbon groups, such as a hetero atom, in the said organic group. The organic group may be any of linear, branched and cyclic.

In the present specification, the trivalent organic group means a trivalent group having three bonding positions in an organic compound.

In addition, the organic group may form a cyclic structure, may form a cyclic structure, and may form a bond including a hetero atom so long as the effect of the invention is not impaired.

Specifically, the bond containing hetero atoms, such as an oxygen atom, a nitrogen atom, and a silicon atom, is mentioned. Specific examples include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N = C (-A)-,-C (= NA) -A represents a hydrogen atom or an organic group), and a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, etc. are mentioned, It does not limit this.

The cyclic structure may include the aforementioned aromatic ring, aliphatic ring, and the like, and may be monocyclic or polycyclic.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl groups.

In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and especially cyclopentyl group, cyclohexyl group, and the like, but is not limited thereto.

In one embodiment of the present specification, l is 3 or more.

In one embodiment of the present specification, X is S.

In another exemplary embodiment, X is a haloalkyl group.

In another embodiment of the present specification, X is NR.

In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and are each independently a halogen substituted aromatic ring.

In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and are each independently a fluorine-substituted aromatic hydrocarbon ring.

In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and are each independently NRR.

In another exemplary embodiment, Y1 and Y2 are each a fluorine substituted phenyl group. Specifically, 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl and the like are not limited thereto.

In one embodiment of the present specification, the compound represented by Formula 4 may be represented by any one of the following structures.

In the above structure, X, 1 and R are the same as defined in the formula (4).

According to an exemplary embodiment of the present specification, Z in Chemical Formula 5 may be represented by any one of the following Chemical Formulas 5-1 to 5-4.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-1 to 5-4,

L2 To L8 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -CO-; Or -SO _2- ,

R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a, b, c, f, h, i and j are each an integer of 1 to 4,

d, e and g are each an integer of 1 to 3,

k is an integer from 1 to 6,

When a, b, c, d, e, f, g, h, i, j and k are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.

In one embodiment of the present specification, L1 is CO.

In another exemplary embodiment, L1 is SO ₂ .

In another exemplary embodiment, L1 is S.

In another embodiment, L2 is CO.

In another exemplary embodiment, L2 is SO ₂ .

In another embodiment, L2 is S.

In one embodiment of the present specification, L3 is CO.

In another exemplary embodiment, L3 is SO ₂ .

In another embodiment, L3 is S.

In one embodiment of the present specification, L4 is CO.

In another exemplary embodiment, L4 is SO ₂ .

In one embodiment of the present specification, L5 is a direct bond.

In another embodiment, L6 is a direct bond.

In one embodiment of the present specification, L7 is a direct bond.

In one embodiment of the present specification, R10 to R20 are hydrogen.

In one embodiment of the present specification, R16 is a halogen group.

In another exemplary embodiment, R16 is fluorine.

In addition, in an exemplary embodiment of the present specification, the brancher represented by Chemical Formula 5 may be represented by any one of the following structures.

In one embodiment of the present specification, the weight average molecular weight of the polymer is 500 g / mol to 2,000,000 g / mol. When the weight average molecular weight of the polymer is in the above range, the mechanical properties of the electrolyte membrane including the polymer are not lowered, and the solubility of the polymer may be maintained to facilitate the preparation of the electrolyte membrane.

In one embodiment of the present specification, the first monomer represented by Chemical Formula 1 and the second monomer different from each other and having at least one sulfonic acid group may constitute a random polymer.

In this case, the polymer including the monomer represented by the formula (1) has the structure of-[CR1R2] _n -A in the form of a pendant (pendant), so that the A functional groups in the polymer are easily phase-separated to facilitate ion separation Can be formed. Therefore, the effect of improving the ionic conductivity of the polymer electrolyte membrane can be expected.

In one embodiment of the present specification, the content of the first monomer represented by Chemical Formula 1 in the polymer is 1 mol% to 99 mol% based on the total content of the polymer, and different from each other with the first monomer, at least The content of the second monomer having one sulfonic acid group is 1 mol% to 99 mol% based on the total content of the polymer. In one embodiment of the present specification, the content of the first monomer represented by Chemical Formula 1 in the polymer is 50 mol% to 99 mol%, different from the first monomer, and a second having at least one sulfonic acid group. The content of monomers is from 1 mol% to 50 mol%, based on the total content of the polymer.

In one embodiment of the present specification, the polymer including the first monomer represented by Formula 1 and the second monomer different from the first monomer and having at least one sulfonic acid group is a random polymer.

In another embodiment of the present specification, the polymer includes a hydrophilic block and a hydrophobic block, and the hydrophilic block is a block polymer including a first monomer represented by Chemical Formula 1.

In one embodiment of the present specification, the hydrophilic block includes a first monomer represented by Formula 1 and a second monomer having at least one sulfonic acid group.

In one embodiment of the present specification, the content of the first monomer in the hydrophilic block is 1 mol% to 99 mol%, different from the first monomer, the content of the second monomer having at least one sulfonic acid group Silver is 1 mol% to 99 mol% based on the total content of the polymer. In one embodiment of the present specification, the content of the first monomer represented by Formula 1 in the hydrophilic block is 50 mol% to 99 mol%, different from the first monomer, having at least one sulfonic acid group The content of the second monomer is from 1 mol% to 50 mol%, based on the total content of the polymer.

In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the block polymer at a molar ratio of 1: 0.1 to 1:10. In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the block polymer in a molar ratio of 1: 0.1 to 1: 2. In another exemplary embodiment, the hydrophilic block and the hydrophobic block are included in the block polymer at a molar ratio of 1: 0.8 to 1: 1.2. In this case, the ion transport ability of the block polymer can be raised.

In an exemplary embodiment of the present specification, the monomer represented by Chemical Formula 1 in the hydrophilic block is contained in an amount of 0.01 mol% to 100 mol% based on the hydrophilic block.

In one embodiment of the present specification, the number average molecular weight of the hydrophilic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.

In one embodiment of the present specification, the number average molecular weight of the hydrophobic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.

According to the exemplary embodiment of the present specification, in the case of the block polymer, the partition and division of the hydrophilic block and the hydrophobic block are clear, so that phase separation is easy, and ion transfer may be easy. According to one embodiment of the present specification, when the monomer represented by Chemical Formula 1 is included, the hydrophilic block and the hydrophobic block are more clearly distinguished, and thus the ion transfer effect may be superior to that of the conventional polymer.

The block polymer refers to a polymer in which one block and one or more blocks different from the block are connected to each other by a main chain of the polymer.

In one embodiment of the present specification, the block polymer may include a hydrophilic block and a hydrophobic block. Specifically, in one exemplary embodiment, the block polymer may include a hydrophilic block and a hydrophobic block including the monomer represented by Chemical Formula 1.

By “hydrophilic block” herein is meant a block having an ion exchange group as a functional group. Wherein the functional groups are ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M + , and -PO ₃ ^2- 2M ⁺ the group consisting of It may be at least one selected from. Here, M may be a metallic element. That is, the functional group may be hydrophilic.

As used herein, the term "block having an ion exchange group" means a block containing an average of 0.5 or more represented by the number of ion exchange groups per structural monomer constituting the block, and an average of 1.0 or more ions per structural monomer. It is more preferable to have an exchanger.

By “hydrophobic block” herein is meant the polymer block which is substantially free of ion exchange groups.

The term "block having substantially no ion exchange group" in the present specification means a block having an average of less than 0.1 represented by the number of ion exchange groups per structural monomer constituting the block, and more preferably 0.05 or less on average. It is more preferable if it is a block which does not have an ion exchange group at all.

In addition, the present disclosure provides a polymer electrolyte membrane including the polymer described above.

In the case of including a polymer including a monomer derived from the compound according to an exemplary embodiment of the present specification, it has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the electrolyte membrane.

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 one embodiment of the present specification may be prepared using materials and / or methods known in the art, except for including a polymer including a monomer derived from the compound.

According to an exemplary embodiment of the present specification, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.7 S / cm or less. In another exemplary embodiment, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less.

In one embodiment of the present specification, the ionic conductivity of the polymer electrolyte membrane may be measured under humidification conditions. In this specification, the humidification condition may mean 10% to 100% relative humidity (RH).

In addition, in an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5.0 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.

In one embodiment of the present specification, the thickness of the polymer electrolyte membrane is 1 μm to 500 μm. The polymer electrolyte membrane having the above range thickness lowers electric short and crossover of electrolyte material, and may exhibit excellent cation conductivity characteristics.

In one embodiment of the present specification, the substrate; And it provides a reinforcing film comprising the polymer described above.

In one embodiment of the present specification, the 'reinforcement membrane' is an electrolyte membrane including a substrate that is a reinforcing material, and a membrane capable of exchanging ions, and includes a substrate, an ion exchange membrane, an ion transfer membrane, and an ion conductive membrane. , Separator, ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion transfer electrolyte membrane or ion conductive electrolyte membrane and the like.

In the present specification, the substrate may mean a support having a three-dimensional network structure, and the reinforcing film including the substrate and the polymer may include one surface of the polymer, a surface facing the surface, and a pore region inside the substrate. It may mean that it is included in at least part of. That is, the reinforcing film of the present specification may be provided in a form in which the polymer is impregnated into the substrate.

The polymer is the same as described above.

In the case of the hydrocarbon-based ion transport membrane, the ion transfer capacity is inferior to that of the fluorine-based separator, and the chemical resistance is weak. Therefore, the reinforcing membrane according to the exemplary embodiment of the present specification includes a polymer including the unit represented by Chemical Formula 1, has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the reinforcing membrane.

In addition, the reinforcing film according to the exemplary embodiment of the present specification may include a substrate, thereby increasing chemical resistance and durability, and thus improving the life of the device.

In one embodiment of the present specification, the substrate is one or two species in the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene (PE) and polyvinylidene difluoride (PVDF) Is selected.

In one embodiment of the present specification, the content of the polymer is 10 parts by weight to 99 parts by weight with respect to 100 parts by weight of the reinforcing film.

In another exemplary embodiment, the polymer content is 10 parts by weight to 99 parts by weight with respect to 100 parts by weight of the reinforcing film, and the content of the substrate is 1 part by weight to 90 parts by weight. As the content of the substrate increases, the crossover of vanadium ions may be reduced, and as the content of the polymer increases, the performance of the battery may be improved.

Therefore, when the content of the substrate and the polymer according to one embodiment of the present specification is in the above range, it is possible to reduce the crossover of vanadium ions while maintaining the performance of the battery.

 According to an exemplary embodiment of the present specification, the ion conductivity of the reinforcing film is 0.001 S / cm or more and 0.5 S / cm or less. In another exemplary embodiment, the ion conductivity of the reinforcing film is 0.001 S / cm or more and 0.3 S / cm or less.

In the present specification, the ion conductivity may be measured under the same conditions as the aforementioned method.

Further, in one embodiment of the present specification, the ion exchange capacity (IEC) value of the reinforcing membrane is 0.01 mmol / g to 5.0 mmol / g. When the ion exchange capacity is in the range, an ion channel in the reinforcing film is formed, and the polymer may exhibit ion conductivity.

In one embodiment of the present specification, the thickness of the reinforcement film is 0.01 μm to 10,000 μm. The thickness of the reinforcement film may reduce the electric short and the crossover of the electrolyte material, and may exhibit excellent cationic conductivity characteristics.

The present disclosure also provides a method for preparing a substrate; And it provides a method for producing a strengthening film comprising the step of impregnating the substrate with a polymer comprising a unit represented by the formula (1).

Impregnation in the present specification means that the polymer permeates into the substrate. In the present specification, the impregnation may be performed by dipping the substrate into the polymer, using a slot dye coating, bar casting, or the like.

In the present specification, immersion may be expressed in terms such as dip coating or dipping method.

In one embodiment of the present specification, the reinforcing film may have a directionality. Specifically, in one embodiment of the present specification, the substrate may be manufactured by uniaxial stretching or biaxial stretching, and the orientation of the substrate by the stretching may determine the orientation of the reinforcing film. Therefore, the reinforcing film according to the exemplary embodiment of the present specification may have a directionality of the machine direction (MD) and the vertical direction of the machine direction (MD), and the reinforcing film may be stressed and elongated according to the direction. The physical properties of can represent a difference.

The present disclosure also provides a method for preparing a substrate; And it provides a method for producing a reinforcing film comprising the step of immersing the substrate in the polymer.

In the present specification, the substrate and the polymer are as described above.

The present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.

The present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described reinforcement film provided between the anode and the cathode.

Membrane-electrode assembly (MEA) is an electrode (cathode and anode) in which the electrochemical catalytic reaction between 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 thermocompression bonding at 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−). 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 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.

In the present specification, the membrane-electrode assembly includes the aforementioned polymer electrolyte membrane or includes a reinforcement membrane.

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 (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 oxidizing agent, and may be used by injecting oxygen or air into the pump 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.

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.

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.

In another embodiment, 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 reinforcing film according to an embodiment of the present disclosure provided between the positive electrode and the negative electrode 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, thereby causing charge and discharge at the anode and the cathode.

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.

< Example  >

Example 1 .

Using the compound, a sulfonate compound according to one embodiment of the present specification was synthesized.

Biphenol (4,4'-Biphenol) and 4,4'-difluorobenzophenone (4,4'-Difluorobenzophenone) and the sulfonate compound according to an embodiment of the present disclosure synthesized for 4 hours at 140 ℃ The mixture was polymerized at 190 ° C. for 48 hours to polymerize using N-methyl-2-piperidone (NMP) as a solvent. After that, the mixture was cooled to room temperature and precipitated in ethanol to obtain a polymer resin.

15 wt% solution (solvent DMAc) was used to prepare a resin-coated ion-transfer membrane, which was then dried in a 110 ° C. vacuum oven for 24 hours. The ion transfer membrane was immersed in 10 wt / wt% sulfuric acid (H ₂ SO ₄ ) solution at 80 ° C. for 24 hours, rinsed with distilled water (DI water) several times, and then ion conductivity was measured. The counterion of sulfonic acid was replaced by H ⁺ rather than K ⁺ .

Example  2.

Biphenol (4,4'-Biphenol), 4,4'-Difluorobenzophenone (4,4'-Difluorobenzophenone) and 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (6F- Diol) (2,2-Bis (4-hydroxyphenyl) -hexafluoropropane (6F-diol)) and a sulfonate-based compound according to one embodiment of the present specification synthesized with 3,3'-disulfonate-4,4 ' -Difluorophenyl sulfone disodium salt (3,3'-disulfonated-4,4'-difluorophenyl sulfone disodium salt) [DFSS] The compound was polymerized at 140 ℃ for 4 hours, 190 ℃ 48 hours to N-methyl-2 -Polymerized using piperidone (NMP) as a solvent, after cooling to room temperature sufficiently precipitated in ethanol to obtain a polymer resin.

A 10 wt% solution (solvent DMAc) was made of the synthesized resin, and the solution was coated to prepare an ion transfer membrane, which was dried in a vacuum oven at 110 ° C for 24 hours. The ion transfer membrane was immersed in 10 wt / wt% sulfuric acid (H ₂ SO ₄ ) solution at 80 ° C. for 24 hours, rinsed with distilled water (DI water) several times, and then ion conductivity was measured. The counterion of sulfonic acid was replaced by H ⁺ rather than K ⁺ .

< Comparative example >

Comparative example  One.

Biphenol (4,4'-Biphenol) and bis (4-fluorophenyl) sulfone (Bis (4-fluorophenyl) sulfone) and 2-((2,4-difluorophenyl) thio) -1,1, 2,2-tetrafluoroethane-1-sulfon sodium salt (2-((2,4-difluorophenyl) thio) 1,1,2,2-tetrafluoroethane-1-sulfone sodium salt) at 140 ° C. for 4 hours, The polymerization was carried out at 180 ° C. for 24 hours, and polymerization was performed using N-methyl-2-piperidone (NMP) as a solvent. After that, the mixture was cooled to room temperature and precipitated in ethanol to obtain a polymer resin.

A 20 wt% solution (solvent DMAc) was made of the synthesized resin, and the solution was coated to prepare an ion transfer membrane, and dried in a vacuum oven at 110 ° C. for 24 hours. The ion transfer membrane was immersed in 10 wt / wt% sulfuric acid (H ₂ SO ₄ ) solution at 80 ° C. for 24 hours, rinsed with distilled water (DI water) several times, and then ion conductivity was measured. The counterion of sulfonic acid was replaced by H ⁺ rather than K ⁺ .

The molecular weight of the resultant of Example 1 and Comparative Example 1 was measured and shown in Table 1 below.

Molecular weight analysis was performed via GPC equipment. PL mixed Bx2 was used as a column and DMF / 0.05M LiBr (filtered with 0.45 μm) was used as a solvent. It was measured at a flow rate of 1.0 ml / min and a sample concentration of 1 mg / ml. The sample was injected with 100ul and the column temperature was set at 65 ° C. Waters RI detector was used as the detector and the reference was set to PS. Data processing was performed through the Empower3 program.

Example 1 A GC mass spectrometry graph of an ion exchange membrane to which a polymer is applied is shown in FIG. 4, and a GC mass spectrometry graph of an ion exchange membrane to which a Comparative Example 1 polymer is applied is shown in FIG. 5.

Mw (g / mol ) Target IEC ( meq / g) Example  One 3.19ⅹ10 ⁵ 1.76 Comparative example  One 9.61ⅹ10 ⁵ 1.78

In the ion exchange membrane to which the sulfide linkage moiety sulfonic acid monomer is applied from the results of Table 1, FIG. 4 and FIG. Since the sulfonic acid group is pyrolyzed in a section of 450 degrees, it can be confirmed that the thermal stability of the ion exchange membrane of Example 1 is excellent. 4 and 5 indicate the intensity (%).

Comparative Example 2.

The polymer of Comparative Example 2 was synthesized in the same manner, except that the monomer was used instead of the monomer used in Examples 1,2 and Comparative Example 1.

Table 2 shows the results of comparative analysis of physical properties and performance of the ion exchange membrane to which the polymers prepared in Example 2 and Comparative Example 2 are applied.

Target IEC (meq / g) Proper IEC
( meq / g) Ion conductivity
(S / cm)
@ RH100% 25 ^o C MEA performance
FS _Current Density
(mA / cm ² @ 0.6V) / OCV
32% RH Water uptake
(%) Example  2 1.91 1.90 0.213 1149 (1142) / 0.906-0.907 43.53 Comparative example  2 1.74 1.57 0.060 - 120.11

As shown in Table 2, it can be confirmed that the ion exchange membrane to which the polymer of Example 2 is applied is superior to the MEA performance under IEC, ion conductivity, and low-humidity conditions, compared to the ion exchange membrane to which the polymer of Comparative Example 2 is applied. In addition, since the water uptake can be reduced, it can be confirmed that the MEA has a suitable mechanical durability.

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 (21)

A first monomer represented by Formula 1; And
A polymer different from the first monomer and comprising a second monomer selected from the following structures:

[Formula 1]

In Chemical Formula 1,
A is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , -PO ₃ ^2- 2M ⁺ , —O (CF ₂ ) _m SO ₃ H, —O (CF ₂ ) _m SO ₃ ^- M ⁺ , —O (CF ₂ ) _m COOH, —O (CF ₂ ) _m COO ^- M ⁺ , —O (CF _{2 ) m PO 3 H 2, -O} (CF 2) m PO 3 H - M + , or -O (CF _{2) m} PO ₃ and ^2- 2M ^+,
m is an integer from 1 to 6,
M is a group 1 element,
R1 and R2 are the same as or different from each other, and each independently a halogen group,
n is an integer from 1 to 10,
When m and n are two or more, the structures in two or more parentheses are the same or different from each other. The method according to claim 1,
A is -SO ₃ H or -SO ₃ ^- M ⁺ in which one polymer. The method according to claim 1,
The first monomer represented by Chemical Formula 1 is a polymer represented by any one of the following Chemical Formulas 1-1 to 1-9:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

. delete The method according to claim 1,
Wherein the second monomer is derived from a compound represented by one of the following Chemical Formulas 2-1 to 2-4, 3-1, and 3-2:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 3-1]

[Formula 3-2]

In Chemical Formulas 2-2, 2-4 and 3-2,
A1 'and A2' are the same as or different from each other, and are each independently a halogen group. The method according to claim 1,
The polymer is a polymer comprising a brancher derived from a compound represented by the formula (4) or a brancher represented by the formula (5):
[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,
X is S; O; CO; SO; SO ₂ ; NR; Hydrocarbon-based or fluorine-based conjugates,
l is an integer from 0 to 100,
when l is 2 or more, two or more X are the same as or different from each other,
Y1 and Y2 are the same as or different from each other, and each independently NRR; An aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,
R is an aromatic ring substituted with a halogen group; Or an aliphatic ring substituted with a halogen group,
Z is a trivalent organic group. The method according to claim 6,
The brancher represented by Formula 5 is any one of the following structures:

,

,

,

,

,

,

,

. The method according to claim 1,
The polymer having a weight average molecular weight of 500 g / mol to 2,000,000 g / mol. The method according to claim 1,
Wherein said polymer is a random polymer. The method according to claim 1,
The polymer comprises a hydrophilic block and a hydrophobic block,
The hydrophilic block is a polymer that is a block polymer comprising a first monomer represented by the formula (1). The method according to claim 10,
The hydrophilic block and the hydrophobic block in the block polymer is included in a molar ratio of 1: 0.1 to 1: 10. A polymer electrolyte membrane comprising the polymer according to any one of claims 1 to 3 and 5 to 11. materials; And
Reinforcement film containing the polymer according to any one of claims 1 to 3 and 5 to 11. The method according to claim 12,
Ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm to 0.7 S / cm It is a polymer electrolyte membrane. The method according to claim 12,
The ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g polymer electrolyte membrane. Anode; Cathode; And a polymer electrolyte membrane of claim 12 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
A polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack. A cathode cell comprising an anode and an anode electrolyte solution;
A cathode cell comprising a cathode and a cathode electrolyte; And
Redox flow battery comprising the polymer electrolyte membrane of claim 12 provided between the positive electrode and the negative electrode cell. Anode; Cathode; And a reinforcing film of claim 13 provided between the anode and the cathode. At least two membrane-electrode assemblies according to claim 19;
A stack comprising a bipolar plate provided between the membrane-electrode assemblies;
A fuel supply unit supplying fuel to the stack; And
A polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack. A cathode cell comprising an anode and an anode electrolyte solution;
A cathode cell comprising a cathode and a cathode electrolyte; And
Redox flow battery comprising the reinforcing film of claim 13 provided between the positive electrode and the negative electrode cell.

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