KR102672160B1 - Polymer, polymer separation membrane using same, membrane electrode assembly, fuel cell and redox flow cell using same - Google Patents

Abstract

The present specification is a polymer comprising a hydrophilic block and a hydrophobic block, wherein the hydrophilic block includes a unit represented by Formula 1, and the hydrophobic block includes a unit represented by Formula 2, a polymer separator containing the same, and the same. It relates to a membrane electrode assembly, fuel cell, and redox flow battery including.

Description

Polymer, polymer separator containing the same, membrane electrode assembly containing the same, fuel cell and redox flow battery {POLYMER, POLYMER SEPARATION MEMBRANE USING SAME, MEMBRANE ELECTRODE ASSEMBLY, FUEL CELL AND REDOX FLOW CELL USING SAME}

This specification relates to polymers, polymer separators containing the same, membrane electrode assemblies containing the same, fuel cells, and redox flow batteries.

Separator materials for fuel cells have high ionic conductivity, and at the same time, to prevent a decrease in cell efficiency during operation, 1) prevention of crossover of electrolyte materials, 2) strong chemical resistance during cell operation, 3) strengthening of mechanical properties, 4 ) It must have characteristics such as low swelling ratio. Currently, most fuel cell separator materials use Nafion. Nafion has high ionic conductivity and good thermal and mechanical properties, but has the disadvantages of high price, methanol crossover, and increased membrane resistance when thickness increases to secure mechanical properties. Therefore, the development of a material that has both the high ionic conductivity of Nafion and the mechanical properties of hydrocarbons is required.

US Patent Application Publication No. 2008-0241626

The purpose of the present invention is to provide a polymer, a polymer separator containing the same, a membrane electrode assembly containing the same, a fuel cell, and a redox flow battery.

An exemplary embodiment of the present specification provides a polymer comprising a hydrophilic block and a hydrophobic block, wherein the hydrophilic block includes a unit represented by the following formula (1), and the hydrophobic block includes a unit represented by the following formula (2) do.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

L1 is direct bonding; -S-; or -O-,

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 ^2- 2M ⁺ ,

m is an integer from 2 to 6, M is a group 1 element,

R1 is hydrogen; halogen group; or a hydroxy group,

k is an integer from 0 to 3, and when k is an integer of 2 or more, the substituents in parentheses are the same or different from each other,

R2 and R3 are the same or different from each other and are each independently a halogen group,

n is an integer from 2 to 10, and when n is an integer of 2 or more, the structures within the parentheses are the same or different,

X1 is ―SO ₂ ―; or -CO-,

T1 and T2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t1 and t2 are each independently an integer of 0 to 4, and when t1 and t2 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,

means bonding to an adjacent substituent or the main chain of the polymer.

Additionally, an exemplary embodiment of the present specification provides a polymer separation membrane containing the above-described polymer.

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

In addition, another embodiment of the present specification includes two or more of the above-described membrane electrode assemblies; A stack including a bipolar plate provided between the membrane electrode assemblies; A fuel supply unit that supplies fuel to the stack; and a polymer electrolyte fuel cell including an oxidizing agent supply unit that supplies an oxidizing agent to the stack.

Lastly, another embodiment of the present specification is a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell containing a cathode and a cathode electrolyte; And it provides a redox flow battery including the polymer separator of the above-described embodiment provided between the anode cell and the cathode cell.

The polymer according to an exemplary embodiment of the present specification does not require a post-treatment process for purification of the polymer after the polymerization reaction, so the process can be simplified and is economical.

The polymer separation membrane according to an exemplary embodiment of the present specification can achieve high ionic conductivity due to a hydrophilic block containing perfluorosulfonic acid, and lowers water uptake due to the hydrophobic block, allowing for humidification conditions. The mechanical stability of the separator can be increased.

1 is a schematic diagram showing the electricity generation principle of a fuel cell.
Figure 2 is a diagram schematically showing an embodiment of a redox flow battery.
Figure 3 is a diagram schematically showing an embodiment of a fuel cell.
Figure 4 is a diagram showing the ¹ H-NMR spectrum of the polymer prepared according to Example 1.
Figure 5 is a diagram showing the molecular weight distribution of the polymer prepared according to Example 1.
Figure 6 is a diagram showing the ¹ H-NMR spectrum of the polymer prepared according to Example 2.
Figure 7 is a diagram showing the molecular weight distribution of the polymer prepared according to Example 2.
Figure 8 shows the cation conductivity of the manufactured polymer separator.

Hereinafter, this specification will be described in more detail.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

As used herein, “derived” means that a bond in a compound is broken or a new bond is created when a substituent is removed, and a unit derived from the compound may mean a unit connected to the main chain of the polymer. The unit may be included in the main chain within the polymer to constitute the polymer.

In this specification, “unit” refers to a repeating structure in which monomers are included in a polymer, and refers to a structure in which monomers are combined within the polymer through polymerization.

In this specification, “including a unit” means included in the main chain within the polymer.

As used herein, “separator” refers to a membrane capable of exchanging ions, including a membrane, ion exchange membrane, ion transport membrane, ion conductive membrane, ion exchange separator, ion transport separator, ion conductive separator, ion exchange electrolyte membrane, ion transport. Includes an electrolyte membrane or an ion conductive electrolyte membrane.

In one embodiment of the present invention, a polymer comprising a hydrophilic block and a hydrophobic block, wherein the hydrophilic block includes a unit represented by the following formula (1), and the hydrophobic block includes a unit represented by the following formula (2) provides.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

L1 is direct bonding; -S-; or -O-,

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 ^2- 2M ⁺ ,

m is an integer from 2 to 6, M is a group 1 element,

R1 is hydrogen; halogen group; or a hydroxy group,

k is an integer from 0 to 3, and when k is an integer of 2 or more, the substituents in parentheses are the same or different from each other,

R2 and R3 are the same or different from each other and are each independently a halogen group,

n is an integer from 2 to 10, and when n is an integer of 2 or more, the structures within the parentheses are the same or different,

X1 is ―SO ₂ ―; or -CO-,

T1 and T2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t1 and t2 are each independently an integer of 0 to 4, and when t1 and t2 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,

means bonding to an adjacent substituent or the main chain of the polymer.

The polymer of the present specification does not require a post-treatment process for purification of the polymer, so the process can be simplified and is economical in terms of cost.

In addition, the polymer manufactured by the manufacturing method according to an exemplary embodiment of the present specification transfers ions through a hydrophilic block and secures mechanical properties through a hydrophobic block, while containing sulfuric acid (- High ionic conductivity can be imparted through the introduction of perfluorosulfonic acid (ex, -CF ₂ CF ₂ SO ₃ H), a super acid, instead of SO ₃ H).

Generally, for the synthesis of polymers containing perfluorosulfonic acid, a method is used in which the polymer has a halogen element (ex, Br, I) in its main chain or side chain and a catalytic reaction using Cu or Pd is used. . In this case, two or more reaction steps are required to polymerize the polymer and introduce functional groups, and an additional process to remove the metal catalyst used in the catalytic reaction is necessary. Additionally, the reaction of more than an equivalent amount of chemicals is required to introduce perfluorosulfonic acid. However, using a monomer into which perfluorosulfonic acid is introduced, as in one embodiment of the present specification, has the advantage of simplifying the reaction process.

The unit represented by Formula 1 according to an exemplary embodiment of the present specification has high reactivity during the polymerization process, and process efficiency can be increased. In addition, a polymer separation membrane manufactured using the above unit can easily form a hydrophilic-hydrophobic phase separation structure. In addition, the polymer separation membrane including the above unit according to an exemplary embodiment of the present specification can efficiently form a hydrophilic channel in the polymer separation membrane by controlling the phase separation structure. In addition, the polymer separator containing the above units has excellent ionic conductivity. Additionally, the unit is thermally and chemically stable.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; hydroxyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl group; It means that it is substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituents. For example, “a substituent group in which two or more substituents are connected” means an alkyl group substituted with a halogen group, an aryl group substituted with an alkyl group, an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heteroaryl group substituted with an alkyl group, or an aryl group substituted with an aryl group. There are heteroaryl groups substituted with heteroaryl groups, heteroaryl groups substituted with heteroaryl groups, etc., but it is not limited thereto.

In this specification, the term "substitution" means changing a hydrogen atom bonded to a carbon atom of a compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, 2 In the case of more than one substitution, two or more substituents may be the same or different from each other.

As used herein, “hydrophilic block” refers to a block having an ion exchange group as a functional group. Here, the functional group 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 ) _w SO ₃ H, ―O(CF ₂ ) _w SO ₃ ^- M ⁺ , ―O(CF ₂ ) _w COOH, ―O(CF ₂ ) _w COO ^- M ⁺ , ―O(CF ₂ ) _w PO ₃ H ₂ , ―O(CF ₂ ) _w PO ₃ H ^- M ⁺ and ―O(CF ₂ ) _w PO ₃ ^2- 2M ⁺ It may be at least one selected from the group consisting of. Here, M is a group 1 element, and w may have a range of 1<w<10. That is, the functional group may be hydrophilic.

In this specification, “a block having an ion exchange group” means a block containing an average of 0.5 or more ion exchange groups, expressed as the number of ion exchange groups per structural monomer constituting the block, and an average of 1.0 or more per structural monomer. It is more preferable to have an ion exchanger.

As used herein, “hydrophobic block” refers to the polymer block substantially free of ion exchange groups.

In this specification, “a block substantially free of ion exchange groups” means a block with an average of less than 0.1 ion exchange groups, expressed in terms of the number of ion exchange groups per structural monomer constituting the block, and an average of 0.05 or less is more preferable. , it is more preferable if it is a block that does not have any ion exchange group.

In this specification, the halogen group may be F, Cl, Br, or I.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. According to one embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, and n-pentyl. , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. It is not limited to this.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include 4,5-trimethylcyclohexyl and 4-tert-butylcyclohexyl, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but may have 6 to 30 carbon atoms, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may include a phenyl group, a biphenyl group, and a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, etc., but is not limited thereto.

In the present specification, the heteroaryl group contains one or more atoms other than carbon, that is, heteroatoms. Specifically, the heteroaryl group may include one or more atoms selected from the group consisting of N, P, O, S, Si, etc. You can. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and according to one embodiment, the number of carbon atoms of the heteroaryl group is 2 to 20. The heteroaryl group may be monocyclic or polycyclic. Examples of heteroaryl groups include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Triazinyl group, triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, etc., but are not limited thereto.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n. -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, etc., but are not limited thereto.

According to an exemplary embodiment of the present specification, the hydrophilic block may include a unit represented by Formula 1.

According to an exemplary embodiment of the present specification, R1 is hydrogen; It is a halogen group or a hydroxy group.

According to an exemplary embodiment of the present specification, L1 is a direct bond; -S-; Or -O-.

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

According to an exemplary embodiment of the present specification, L1 is -S-.

According to an exemplary embodiment of the present specification, L1 is -O-.

According to an exemplary embodiment of the present specification, 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 ^2- 2M ⁺ .

According to an exemplary embodiment of the present specification, A is -SO ₃ H, -SO ₃ ^{-M +} , -O(CF ₂ ) _m SO ₃ H, or -O(CF ₂ ) _m SO ₃ ^- M ⁺ .

According to an exemplary embodiment of the present specification, A is -SO ₃ H, or -SO ₃ ^{-M +} .

According to an exemplary embodiment of the present specification, A is -O(CF ₂ ) _m SO ₃ H, or -O(CF ₂ ) _m SO ₃ ^{-M +} .

According to an exemplary embodiment of the present specification, A is O(CF ₂ ) _m SO ₃ ^- M ⁺ .

According to an exemplary embodiment of the present specification, when A is -SO ₃ H, -SO ₃ ^{-M +} , -O(CF ₂ ) _m SO ₃ H, or -O(CF ₂ ) _m SO ₃ ^- M ⁺ , a polymer containing the unit represented by Formula 1 can be formed chemically stably.

According to an exemplary embodiment of the present specification, M is a group 1 element.

According to an exemplary embodiment of the present specification, the Group 1 element is Li, Na, or K.

According to an exemplary embodiment of the present specification, R2 and R3 are the same or different from each other and are each independently a halogen group.

According to an exemplary embodiment of the present specification, R2 and R3 are F.

According to an exemplary embodiment of the present specification, k is an integer from 0 to 3, and when k is an integer of 2 or more, the substituents in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, k is 0.

According to an exemplary embodiment of the present specification, m is an integer from 2 to 6.

According to an exemplary embodiment of the present specification, m is 2.

The n is an integer of 2 to 10, and when n is an integer of 2 or more, the structures within the parentheses are the same or different.

According to an exemplary embodiment of the present specification, n is 2.

According to an exemplary embodiment of the present specification, the unit of Chemical Formula 1 may be derived from Chemical Formula 1A below.

[Formula 1A]

In Formula 1A,

R5 to R9 are the same as or different from each other, and are each independently hydrogen; halogen group; or a hydroxy group, and at least two of R5 to R9 are halogen groups; or a hydroxy group,

The definitions of other substituents are the same as in Formula 1.

According to an exemplary embodiment of the present specification, at least two of R5 to R9 are halogen groups.

According to an exemplary embodiment of the present specification, R5 to R9 are the same or different from each other and are each independently hydrogen or F.

According to an exemplary embodiment of the present specification, at least two of R5 to R9 are F.

According to an exemplary embodiment of the present specification, at least two of R5 to R9 are F, and the remainder are hydrogen.

According to an exemplary embodiment of the present specification, R6 and R8 are F, and R5, R7, and R9 are hydrogen.

According to an exemplary embodiment of the present specification, R5 and R7 are F, and R6, R8, and R9 are hydrogen.

According to an exemplary embodiment of the present specification, R6 and R9 are F, and R5, R7, and R8 are hydrogen.

According to an exemplary embodiment of the present specification, Formula 1A may be represented by one selected from the following Formulas 1A-1 to 1A-6.

[Formula 1A-1]

[Formula 1A-2]

[Formula 1A-3]

[Formula 1A-4]

[Formula 1A-5]

[Formula 1A-6]

In Formulas 1A-1 to 1A-6, n, m, and M are as defined in Formula 1.

According to an exemplary embodiment of the present specification, the hydrophobic block may include a unit represented by Formula 2.

According to an exemplary embodiment of the present specification, X1 is a direct bond; ―SO ₂ ―; Or -CO-.

According to an exemplary embodiment of the present specification, X1 is -SO ₂ -; Or -CO-.

According to an exemplary embodiment of the present specification, X1 is a direct bond.

According to an exemplary embodiment of the present specification, X1 is -CO-.

According to an exemplary embodiment of the present specification, X1 is -SO ₂ -.

According to an exemplary embodiment of the present specification, T1 and T2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Or, it is a halogen group, and t1 and t2 are each independently an integer of 0 to 4, and when t1 and t2 are integers of 2 or more, the substituents in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, T1 and T2 are the same or different from each other, and are each independently hydrogen; Or it is a halogen group.

According to an exemplary embodiment of the present specification, T1 and T2 are the same or different from each other and are each independently hydrogen.

According to an exemplary embodiment of the present specification, the unit of Chemical Formula 2 may be derived from Chemical Formula 2A below.

[Formula 2A]

In Formula 2A,

Z1 and Z2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group,

The definitions of other substituents are the same as in Formula 2.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same or different from each other and are each independently hydrogen or deuterium.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same or different from each other and are each independently a halogen group.

According to an exemplary embodiment of the present specification, Z1 and Z2 are F.

In the present specification, each of the hydrophilic blocks may further include a unit derived from a compound represented by the following formula (B1).

[Formula B1]

In the formula B1,

X2 is a direct bond; ―O―; or -S-,

Z3 and Z4 are the same or different from each other, and are each independently a hydroxy group; Or a thiol group,

T3 and T4 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group,

t3 and t4 are each independently integers of 0 to 4, and when t3 and t4 are integers of 2 or more, the substituents in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, X2 is -O-; Or -S-.

According to an exemplary embodiment of the present specification, X2 is a direct bond.

According to an exemplary embodiment of the present specification, X2 is -O-.

According to an exemplary embodiment of the present specification, X2 is -S-.

According to an exemplary embodiment of the present specification, Z3 and Z4 are hydroxy groups.

According to an exemplary embodiment of the present specification, Z3 and Z4 are thiol groups.

According to an exemplary embodiment of the present specification, t3 and t4 are 0.

In the present specification, a polymer is provided in which the hydrophilic block further includes a repeating unit represented by the following formula (3).

[Formula 3]

In Formula 3, X2 to X4 are the same or different from each other and are each independently a direct bond; ―O―; or -S-,

T3 and T4 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group,

t3 and t4 are each independently integers of 0 to 4, and when t3 and t4 are integers of 2 or more, the substituents in parentheses are the same or different from each other,

a1 is the number of repetitions of the unit in the parentheses, and is an integer from 1 to 1,000.

The definitions of other substituents are the same as those in Chemical Formula 1.

According to an exemplary embodiment of the present specification, X2 to X4 are direct bonds.

According to an exemplary embodiment of the present specification, X2 to X4 are the same as or different from each other, and are each independently -O-; Or -S-.

According to an exemplary embodiment of the present specification, X2 is a direct bond, and X3 and X4 are the same as or different from each other, and are each independently -O-; Or -S-.

According to one embodiment of the present specification, X2 is a direct bond, and X3 and X4 are -O-.

According to one embodiment of the present specification, X2 is a direct bond, and X3 and X4 are -S-.

According to an exemplary embodiment of the present specification, X2 to X4 are -O-.

According to an exemplary embodiment of the present specification, X2 to X4 are -S-.

According to an exemplary embodiment of the present specification, t3 and t4 are 0.

According to an exemplary embodiment of the present specification, Formula 3 may be represented by one selected from the following Formulas 3-1 to 3-3.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4, the definitions of substituents are as defined in Formula 3.

In the present specification, each of the hydrophobic blocks may further include a unit derived from a compound represented by the following formula B2.

[Formula B2]

In the formula B2,

X5 is directly bonded; ―O―; or -S-,

Z5 and Z6 are the same or different from each other, and are each independently a hydroxy group; Or a thiol group,

T5 and T6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group,

t5 and t6 are each independently integers of 0 to 4, and when t5 and t6 are integers of 2 or more, the substituents in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, X5 is -O-; Or -S-.

According to an exemplary embodiment of the present specification, X5 is a direct bond.

According to an exemplary embodiment of the present specification, X5 is -O-.

According to an exemplary embodiment of the present specification, X5 is -S-.

According to an exemplary embodiment of the present specification, Z5 and Z6 are hydroxy groups.

According to an exemplary embodiment of the present specification, Z5 and Z6 are thiol groups.

According to an exemplary embodiment of the present specification, t5 and t6 are 0.

In the present specification, a polymer is provided in which the hydrophobic block further includes a repeating unit represented by the following formula (4).

[Formula 4]

In Formula 4, X5 to X7 are the same or different from each other and are each independently a direct bond; ―O―; or -S-,

T5 and T6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t5 and t6 are each independently an integer of 0 to 4, and when t5 and t6 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,

a2 is the number of repetitions of the unit in the parentheses, and is an integer from 1 to 1,000.

Other definitions are the same as those in Chemical Formula 2.

According to an exemplary embodiment of the present specification, X5 to X7 are direct bonds.

According to an exemplary embodiment of the present specification, X5 to X7 are the same as or different from each other, and are each independently -O-; Or -S-.

According to an exemplary embodiment of the present specification, X5 is a direct bond, X6 and X7 are the same or different from each other, and are each independently -O-; Or -S-.

According to one embodiment of the present specification, X5 is a direct bond, and X6 and X7 are -O-.

According to one embodiment of the present specification, X2 is a direct bond, and X6 and X7 are -S-.

According to an exemplary embodiment of the present specification, X5 to X7 are -O-.

According to an exemplary embodiment of the present specification, X5 to X7 are -S-.

According to an exemplary embodiment of the present specification, t5 and t6 are 0.

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

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4, the definitions of substituents are as defined in Formula 4.

According to one embodiment of the present specification, means bonding to an adjacent substituent or the main chain of the polymer.

According to an exemplary embodiment of the present specification, the polymer may be a random polymer containing the above-described units.

According to an exemplary embodiment of the present specification, the polymer may be a block polymer including a hydrophilic block and a hydrophobic block.

According to an exemplary embodiment of the present specification, the polymer may further include a brancher.

In this specification, “Brancher” serves to connect or crosslink polymer chains.

According to an exemplary embodiment of the present specification, the brancher may serve to connect or crosslink polymer chains.

According to an exemplary embodiment of the present specification, in the case of a polymer further including the brancher, the brancher can directly constitute the main chain of the polymer and improve the mechanical integration of the thin film. For example, the branched polymer according to an embodiment of the present specification polymerizes a branched hydrophobic block that does not contain acid substituents and a branched hydrophilic block that contains acid substituents. By doing so, the brancher directly constructs the main chain of the polymer without performing post-sulfonation or cross-linking of the sulfonated polymer, and provides mechanical stability for the thin film. The hydrophobic block, which maintains integration, and the hydrophilic block, which provides ionic conductivity to the thin film, can alternately form chemical bonds.

According to an exemplary embodiment of the present specification, the polymer may further include a brancher represented by the following formula (5).

[Formula 5]

In Formula 5,

Z is a trivalent organic group.

In this specification, “organic groups” include alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, etc. The organic group may contain bonds or substituents other than hydrocarbon groups such as heteroatoms. Additionally, the organic group may be linear, branched, or cyclic.

As used herein, “trivalent organic group” means a trivalent group having three bonding positions in an organic compound.

Additionally, according to an exemplary embodiment of the present specification, the organic group may form a cyclic structure and may form a bond including a heteroatom as long as the effect of the invention is not impaired. Specifically, a bond containing a heteroatom such as an oxygen atom, a nitrogen atom, or a silicon atom can be mentioned. Specific examples include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N=C(-W)-, -C(=N ⁺ W) -; W represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond, etc., but is not limited thereto.

In the present specification, the cyclic structure may include the above-mentioned aromatic ring, aliphatic ring, etc., and may be monocyclic or polycyclic.

In the present specification, the aromatic ring may be a substituted or unsubstituted aromatic hydrocarbon ring or an aromatic heterocycle, and may be monocyclic or polycyclic.

In the present specification, the aromatic hydrocarbon ring includes monocyclic aromatic rings such as phenyl group, biphenyl group, and terphenyl group, and naphthyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, and tetracenyl group. , polycyclic aromatic rings such as chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, and fluoranthene group, but are not limited thereto. In the present specification, the description of the aryl group above may be applied to the aromatic hydrocarbon ring.

As used herein, an aromatic hetero ring refers to a structure that includes one or more atoms selected from the group consisting of heteroatoms such as N, P, O, S, and Si instead of carbon atoms in the aromatic hydrocarbon ring, The explanation for heteroaryl groups may apply. 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, acridyl 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group , thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, etc., but are not limited to these.

In the present specification, the aliphatic ring may be a substituted or unsubstituted aliphatic hydrocarbon ring or an aliphatic heterocycle, and may be monocyclic or polycyclic.

In the present specification, the description of the above cycloalkyl group may be applied to the aliphatic hydrocarbon ring.

In the present specification, the aliphatic heterocycle refers to a structure containing one or more atoms selected from the group consisting of heteroatoms such as N, P, O, S, Se, Ge, and Si instead of carbon atoms in the aliphatic hydrocarbon ring. it means.

In the present specification, the description of the aromatic heterocycle and aliphatic heterocycle may be applied to the heterocyclic group.

According to an exemplary embodiment of the present specification, Z is a trivalent substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, Z is a trivalent alkyl group.

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

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Formulas 5-1 to 5-4,

L21 to L27 are the same or different from each other and are each independently directly bonded; -S-; -O-; -CO-; or -SO ₂ -,

W11 to W21 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

w1, w2, w3, w6, w8, w9 and w10 are each an integer from 1 to 4, w4, w5 and w7 are each an integer from 1 to 3, w11 is an integer from 1 to 3, and w1 to w11 are each an integer In the case of an integer of 2 or more, the structures within 2 or more parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, L21 is CO.

According to an exemplary embodiment of the present specification, L21 is SO ₂ .

According to an exemplary embodiment of the present specification, L21 is S.

According to an exemplary embodiment of the present specification, L22 is CO.

According to an exemplary embodiment of the present specification, L22 is SO ₂ .

According to an exemplary embodiment of the present specification, L22 is S.

According to an exemplary embodiment of the present specification, L23 is CO.

According to an exemplary embodiment of the present specification, L23 is SO ₂ .

According to an exemplary embodiment of the present specification, L23 is S.

According to an exemplary embodiment of the present specification, L24 is CO.

According to an exemplary embodiment of the present specification, L24 is SO ₂ .

According to an exemplary embodiment of the present specification, L25 is a direct bond.

According to an exemplary embodiment of the present specification, L26 is a direct bond.

According to an exemplary embodiment of the present specification, L27 is a direct bond.

According to an exemplary embodiment of the present specification, W11 to W21 are hydrogen.

According to an exemplary embodiment of the present specification, W11 to W16, and W18 to W21 are each hydrogen.

According to an exemplary embodiment of the present specification, W17 is a halogen group.

According to an exemplary embodiment of the present specification, W17 is fluorine (F).

According to an exemplary embodiment of the present specification, W17 is hydrogen (H).

According to an exemplary embodiment of the present specification, the brancher represented by Formula 5 may be represented by one selected from the following structures.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the polymer is 1,000 g/mol to 1,200,000 g/mol. According to specific embodiments, it is 10,000 g/mol to 1,000,000 g/mol, and more preferably 10,000 g/mol to 800,000 g/mol. When the weight average molecular weight of the polymer is within the above range, the mechanical properties of the polymer separator containing the polymer do not deteriorate, and appropriate solubility of the polymer is maintained, making it easy to manufacture the separator.

According to an exemplary embodiment of the present specification, the polymer may be a block polymer, the hydrophilic block of the block polymer includes a unit represented by Formula 1, and the hydrophobic block of the block polymer includes a unit represented by Formula 2 may include.

According to one embodiment of the present specification, the polymer may be a block polymer, the hydrophilic block of the block polymer includes a repeating unit represented by Formula 3, and the hydrophobic block of the block polymer is represented by Formula 4 May contain repeat units.

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

The hydrophilic block according to an exemplary embodiment of the present specification includes perfluorosulfonic acid and can achieve high ionic conductivity of the polymer separator.

Accordingly, the polymer according to an embodiment of the present specification can control the ion exchange capacity (IEC) in a membrane electrode assembly, fuel cell, or redox flow battery by adjusting the ratio of hydrophilic blocks and hydrophobic blocks. You can.

According to an exemplary embodiment of the present specification, the unit represented by Formula 1 is included in the hydrophilic block in an amount of 0.01 mol% to 100 mol% based on the hydrophilic block.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the hydrophilic block is 1,000 g/mol to 600,000 g/mol. According to specific embodiments, it is 2,000 g/mol to 400,000 g/mol. According to another embodiment, it is 5,000 g/mol to 400,000 g/mol.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the hydrophobic block is 1,000 g/mol to 600,000 g/mol. According to specific embodiments, it is 2,000 g/mol to 400,000 g/mol. According to another embodiment, it is 5,000 g/mol to 400,000 g/mol.

According to an exemplary embodiment of the present specification, in the case of a block polymer, the division and distinction between the hydrophilic block and the hydrophobic block are clear, so phase separation is easy, and ion transfer can be facilitated.

According to an exemplary embodiment of the present specification, when the unit represented by Formula 1 is included, the distinction between the hydrophilic block and the hydrophobic block becomes clearer, and the ion transport effect may be superior to that of conventional polymers.

According to one embodiment of the present specification, the block polymer refers to a polymer composed of one block and one or two or more blocks different from the block connected to each other through the main chain of the polymer.

According to an exemplary embodiment of the present specification, preparing a first monomer containing a unit represented by Formula 1; Preparing a second monomer containing a unit represented by Formula 2; and polymerizing the first and second monomers.

According to an exemplary embodiment of the present specification, preparing a first monomer containing a unit represented by Formula 1; Preparing a second monomer containing a unit represented by Formula 2; It provides a method for producing the above-described polymer, including the step of producing the above-described brancher and polymerizing the first and second monomers and the brancher.

This specification provides a polymer separation membrane containing the above-described polymer.

According to an exemplary embodiment of the present specification, the polymer separator is a polymer, except that the unit represented by Formula 1 is included in the hydrophilic block and the unit represented by Formula 2 is included in the hydrophobic block. It can be manufactured using known materials and/or methods. For example, it can be performed by applying a solution containing the polymer and drying and/or curing.

According to an exemplary embodiment of the present specification, the application may be performed using methods such as tape casting, dip coating, spray coating, and spin coating. there is.

According to an exemplary embodiment of the present specification, the solvent used in the production of the polymer membrane is N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N,N- Dimethylpyrrolidone (N,N-dimethylpyrollidone (NMP)), diphenylsulfone, N,N-dimethylformamide (DMF), etc. can be used, but are limited to these. no.

According to an exemplary embodiment of the present specification, the drying may be performed by heating.

According to an exemplary embodiment of the present specification, the heating means drying through heating.

According to an exemplary embodiment of the present specification, the heating temperature may be 30°C or more and 200°C or less, specifically 50°C or more and 150°C or less.

According to an exemplary embodiment of the present specification, the heating time may be 1 hour or more and 46 hours or less, specifically 5 hours or more and 20 hours or less.

According to an exemplary embodiment of the present specification, the method of manufacturing the polymer separation membrane may further include adding an acid solution to the solution containing the polymer. The acid solution may be hydrochloric acid (HCl).

According to an exemplary embodiment of the present specification, when an acid solution is added to a solution containing the polymer, the metal M of A of Formula 1 may be replaced with H (hydrogen).

According to an exemplary embodiment of the present specification, the heating is preheated at 50°C to 70°C for 2 to 6 hours, dried at 80°C for more than 12 hours, and finally dried in a vacuum oven at 80°C for more than 12 hours. can do.

According to an exemplary embodiment of the present specification, the ionic conductivity of the polymer separator is 0.001 mS/cm to 8 mS/cm. Preferably it is 0.001 mS/cm to 5 mS/cm.

According to an exemplary embodiment of the present specification, the cation conductivity of the polymer separator is 0.001 mS/cm to 8 mS/cm. Preferably it is 0.001 mS/cm to 5 mS/cm.

According to an exemplary embodiment of the present specification, the ionic conductivity (cation conductivity) of the polymer separator can be measured under different humidification conditions. In this specification, humidifying conditions may mean relative humidity (RH) of 10% to 100%.

According to an exemplary embodiment of the present specification, the ionic conductivity can be measured as follows. Before measurement, the polymer membrane was sufficiently immersed in DI water for 24 hours. The separator specimen was cut into 1 × 5 cm ² and the resistance of the membrane was measured using the cell below. Impedance was measured using a Potentioglavano station (SP-240) in the range of 10MHz to 7Hz while submerged in water.

The ionic conductivity of a polymer membrane can be calculated using the measured resistance of the membrane, and the calculation formula is as follows.

Ion conductivity (∂) = l/(R x d)

Here, l is the distance between the two electrodes (1cm), R is the membrane resistance (Ω) measured through SP-240, and d is the thickness of the ion exchange membrane (cm). The unit of ionic conductivity is obtained as S/cm.

In this specification, ionic conductivity may mean cationic conductivity.

According to an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer separator is 0.01 mmol/g to 5.0 mmol/g. When the ion exchange capacity value is within the above range, ion channels are formed in the polymer separator, and the polymer can exhibit excellent ionic conductivity.

According to an exemplary embodiment of the present specification, the thickness of the polymer separator is 1 ㎛ to 500 ㎛. A polymer separator with a thickness in the above range can reduce electrical short and crossover of electrolyte materials, and exhibit excellent cation conductivity characteristics.

This specification also includes an anode; cathode; And it provides a membrane electrode assembly including the above-described polymer separator provided between the anode and the cathode.

As used herein, “membrane electrode assembly (MEA)” refers to an assembly of an electrode (cathode and anode) in which an electrochemical catalytic reaction of fuel and air occurs and a polymer separation membrane in which hydrogen ions are transferred, and consists of an electrode (cathode and anode) It is a single integrated unit with an anode and a separator bonded together.

According to an exemplary embodiment of the present specification, the membrane electrode assembly is in a form in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the polymer separation membrane, and can be manufactured according to a conventional method known in the art. In one example, the cathode; anode; And it can be manufactured by thermo-compression at 100°C to 400°C with the polymer separator positioned between the cathode and the anode in close contact.

According to an exemplary embodiment of the present specification, the anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may further include an anode microporous layer and an anode electrode substrate.

According to an exemplary embodiment of the present specification, 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.

Figure 1 schematically shows the principle of electricity generation in a fuel cell. In a fuel cell, the most basic unit that generates electricity is a membrane electrode assembly (MEA), which consists of a separator 100 and both sides of the separator 100. It consists of an anode (200a) and a cathode (200b) electrode formed in. Referring to FIG. 1 showing the principle of electricity generation in a fuel cell, an oxidation reaction of fuel such as hydrogen or hydrocarbons such as methanol or butane occurs at the anode 200a, generating hydrogen ions (H ⁺ ) and electrons (e ^- ). , hydrogen ions move to the cathode (200b) through the separator 100. At the cathode 200b, hydrogen ions transferred through the separator 100 react with an oxidizing agent such as oxygen and electrons to generate water. This reaction causes the movement of electrons to the external circuit.

The catalyst layer of the anode electrode is where the oxidation reaction of fuel occurs, and a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, and platinum-transition metal alloy is preferred. It can be used effectively.

The catalyst layer of the cathode electrode is where a reduction reaction of the oxidizing agent occurs, and platinum or a platinum-transition metal alloy may be preferably used as a catalyst. The catalysts can be used by themselves as well as supported on a carbon-based carrier.

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst layer can be formed by coating the catalyst ink directly on the separator or on the gas diffusion 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 methods can be used. Catalytic ink may typically consist of a catalyst, polymer ionomer, and solvent.

The gas diffusion layer serves as a current conductor and a passage for reactive gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive substrate. Carbon paper, carbon cloth, or carbon felt may be preferably used as the conductive substrate.

The gas diffusion layer may further include a micropore layer between the catalyst layer and the conductive substrate. The microporous layer can be used to improve the performance of the fuel cell under low humidity conditions, and serves to reduce the amount of water escaping out of the gas diffusion layer to ensure that the polymer separator is sufficiently wet.

An exemplary embodiment of the present specification includes two or more of the above-described membrane electrode assemblies; A stack including a bipolar plate provided between the membrane electrode assemblies; a fuel supply unit that supplies fuel to the stack; and a polymer electrolyte fuel cell including an oxidizing agent supply unit that supplies an oxidizing agent to the stack.

A fuel cell is an energy conversion device that directly converts the chemical energy of fuel into electrical energy. In other words, a fuel cell is a power generation method that uses fuel gas and oxidizer and produces electricity using electrons generated during their oxidation-reduction reaction.

Fuel cells can be manufactured according to conventional methods known in the art using the membrane electrode assembly (MEA) described above. For example, it can be manufactured by consisting of the membrane electrode assembly (MEA) manufactured above and a bipolar plate.

In this specification, the fuel cell includes a stack, a fuel supply unit, and an oxidant supply unit.

Figure 3 schematically shows the structure of a fuel cell. The fuel cell includes a stack 60, an oxidizing agent supply unit 70, and a fuel supply unit 80.

The stack 60 includes one or two or more of the above-described membrane electrode assemblies, and when two or more membrane electrode assemblies are included, it includes a separator interposed between them. The separator prevents the membrane electrode assemblies from being electrically connected and serves to deliver externally supplied fuel and oxidizer to the membrane electrode assembly.

The oxidizing agent supply unit 70 serves to supply the oxidizing agent to the stack 60. Oxygen is typically used as an oxidizing agent, and oxygen or air can be injected with a pump.

The fuel supply unit 80 serves to supply fuel to the stack 60, and includes a fuel tank 81 that stores fuel and a pump 82 that supplies the fuel stored in the fuel tank 81 to the stack 60. It can be configured. As fuel, gaseous or liquid hydrogen or hydrocarbon fuel 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.

According to an exemplary embodiment of the present specification, the above-described effect can be achieved when the polymer separation membrane is used as an ion exchange membrane for a fuel cell.

Additionally, according to an exemplary embodiment of the present specification, an anode cell including an anode and an anode electrolyte; A cathode cell containing a cathode and a cathode electrolyte; And it provides a redox flow battery including the above-described polymer separator provided between the anode cell and the cathode cell.

Redox Flow Battery (Oxidation-Reduction Flow Battery) is a system in which the active materials contained in the electrolyte are oxidized and reduced to charge and discharge. It is an electrochemical storage device that directly stores the chemical energy of the active materials as electrical energy. am. Redox flow batteries use the principle of charging and discharging by exchanging electrons when electrolyte solutions containing active substances in different oxidation states meet across an ion exchange membrane. In general, a redox flow battery consists of a tank containing an electrolyte, a battery cell where charging and discharging occurs, and a circulation pump to circulate the electrolyte between the tank and the battery cell. The unit cell of the battery cell consists of electrodes, electrolyte, and ions. Contains an exchange membrane.

According to an exemplary embodiment of the present specification, the above-described effect can be achieved when the polymer separator is used as an ion exchange membrane of a redox flow battery.

According to an exemplary embodiment of the present specification, a redox flow battery can be manufactured according to a conventional method known in the art, except that it includes the polymer separator.

As shown in FIG. 2, the redox flow battery is divided into an anode cell 32 and a cathode cell 33 by a separator 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 solution is circulated through the pumps 11 and 21, and an oxidation/reduction reaction (i.e., a redox reaction) in which the oxidation number of the ion changes occurs, causing charging and discharging at the anode and cathode.

Hereinafter, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described in detail below. The embodiments of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

<Example 1> Preparation of polymer I using dihydroxy monomer

(z1:y1 = 8:2)

Perfluorinated 3,5-Difluorobenzene monomer in a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, nitrogen inlet, and mechanical stirrer. Add 20.000 g (41.64 mmol), 4,4'-Biphenol 9.692 g (52.05 mmol), and 2.436 g (3.12 mmol) of Sulfone crosslinker, and then add nitrogen using 68 mL of N-Methyl-2-pyrrolidone (NMP) and 30 mL of toluene. The reaction was carried out in an atmosphere using 28.774 g (208.20 mmol) of potassium carbonate as a catalyst. The reaction mixture was stirred in an oil bath at a temperature of 140°C for 3 hours, and water and toluene were removed by reflux distillation. Afterwards, the temperature was raised to 185°C and the reaction was carried out for 24 hours.

After the reaction, the temperature was lowered to room temperature, and the synthesized random polymer solution was slowly dropped into 2000mL HCl Solution (1M) to obtain a precipitate. Only the precipitate was obtained through a glass filter and washed with distilled water. The obtained random polymer was dried in a vacuum oven at 70 °C for 24 hours.

The ¹ H-NMR spectrum and molecular weight distribution of the polymer prepared according to Example 1 are shown in Figures 4 and 5, respectively.

<Example 2> Preparation of polymer using dithiol monomer

(z2:y2 = 8:2)

Perfluorinated 3,5-Difluorobenzene monomer in a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, nitrogen inlet, and mechanical stirrer. Add 10.000 g (20.82 mmol), 4,4'-Thiobisbenzenethiol 6.518 g (26.03 mmol), and 1.218 g (1.56 mmol) of Sulfone crosslinker, and then add nitrogen using 47 mL of N-Methyl-2-pyrrolidone (NMP) and 20 mL of toluene. The reaction was carried out in an atmosphere using 14.387 g (104.10 mmol) of potassium carbonate as a catalyst. The reaction mixture was stirred in an oil bath at a temperature of 140°C for 3 hours, and water and toluene were removed by reflux distillation. Afterwards, the temperature was raised to 185°C and the reaction was carried out for 24 hours.

After the reaction, the temperature was lowered to room temperature, and the synthesized random polymer solution was slowly dropped into 2000mL HCl Solution (1M) to obtain a precipitate. Only the precipitate was obtained through a glass filter and washed with distilled water. The obtained random polymer was dried in a vacuum oven at 70 °C for 24 hours.

The ¹ H-NMR spectrum and molecular weight distribution of the polymer prepared according to Example 2 are shown in Figures 6 and 7, respectively.

<Manufacture of polymer separator>

The polymer prepared in Example 1 was dissolved in DMSO (dimethylsulfoxide) at 35 wt/v% and then filtered through a 5㎛ syringe filter. A polymer separator was prepared by casting the filtered solution on a glass plate, and dried in an oven at 80°C for 12 hours, followed by drying in a vacuum oven at 80°C for 12 hours.

The prepared polymer membrane was separated by placing it in distilled water, and then treated in a 1M hydrochloric acid (HCl) solution at room temperature for 24 hours and in a 1M sulfuric acid (H ₂ SO ₄ ) solution at 80°C for 12 hours. After being washed repeatedly with distilled water, it was kept in distilled water for 24 hours.

Next, the polymer membrane was removed from distilled water and dried in a vacuum oven at 80°C for 12 hours to prepare a polymer membrane. The manufactured polymer separator was in the form of a brown, transparent film.

The calculated ion exchange capacity and cation conductivity of the prepared polymer membrane are shown in Table 1 and Figure 8 below.

IEC(calc.)
(meq/g) Cation conductivity 1
(mS/cm)
@RH30%,70℃ Cation conductivity 2
(mS/cm)
@RH50%,70℃ Cationic conductivity 3
(mS/cm)
@RH80%,70℃ Cation conductivity 4
(mS/cm)
@RH100%,70℃ Example 1 1.45 1.172 x 10 ^-3 3.994 x 10 ^-3 2.228 x 10 ^-2 9.958 x 10 ^-2 Example 2 1.45 1.481 x 10 ^-3 8.651 x 10 ^-3 6.534 x 10 ^-2 1.565 x 10 ^-1

Through examples, it can be confirmed that the synthesis of a polymer containing perfluorosulfonic acid is possible without a post-treatment process for purifying the polymer and the reaction of more than an equivalent amount of chemicals to introduce perfluorosulfonic acid, which simplifies the reaction process. means that is possible.

In addition, through the calculated ion exchange capacity and cation conductivity values, it was confirmed that the polymer of the example can be used as an ion transport membrane.

100: Separator
200a: anode
200b: cathode
10: Anode tank
20: cathode tank
11, 21: pump
31: separator
32: anode cell
33: cathode cell
41: anode electrolyte
42: cathode electrolyte
60: stack
70: Oxidizing agent supply unit
80: fuel supply unit
81: fuel tank
82: pump

Claims (10)

It includes a hydrophilic block, a hydrophobic block, and a brancher represented by the following formula (5),
The hydrophilic block includes a unit represented by the following formula (1),
A polymer wherein the hydrophobic block includes a unit represented by the following formula (2):
[Formula 1]

[Formula 2]

[Formula 5]

In Formulas 1, 2 and 5,
L1 is direct bonding; -S-; or -O-,
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 ^2- 2M ⁺ ,
m is an integer from 2 to 6, M is a group 1 element,
R1 is hydrogen; halogen group; or a hydroxy group,
k is an integer from 0 to 3, and when k is an integer of 2 or more, the substituents in parentheses are the same or different from each other,
R2 and R3 are the same or different from each other and are each independently a halogen group,
n is an integer from 2 to 10, and when n is an integer of 2 or more, the structures within the parentheses are the same or different,
X1 is ―SO ₂ ―; or -CO-,
T1 and T2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t1 and t2 are each independently an integer of 0 to 4, and when t1 and t2 are integers of 2 or more, the substituents in parentheses are the same or different from each other,
Z is is,
means bonding to an adjacent substituent or the main chain of the polymer. In claim 1,
The polymer wherein L1 is -S-. In claim 1,
The A is -O(CF ₂ ) _m SO ₃ H, or -O(CF ₂ ) _m SO ₃ ^{-M +} , m is an integer of 2 to 6, and M is a group 1 element. In claim 1,
The polymer wherein R2 and R3 are F. In claim 1,
The hydrophilic block further includes a repeating unit represented by the following formula (3):
[Formula 3]

In Formula 3,
X2 to X4 are the same or different from each other and are each independently directly bonded; ―O―; or -S-,
T3 and T4 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t3 and t4 are each independently an integer of 0 to 4, and when t3 and t4 are integers of 2 or more, the substituents in parentheses are the same or different from each other,
a1 is the number of repetitions of the unit in the parentheses, and is an integer from 1 to 1,000.
The definitions of other substituents are the same as those in Chemical Formula 1. In claim 1,
A polymer wherein the hydrophobic block further includes a repeating unit represented by the following formula (4):
[Formula 4]

In Formula 4,
X5 to X7 are the same or different from each other and are each independently directly bonded; ―O―; or -S-,
T5 and T6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; or a halogen group, t5 and t6 are each independently an integer of 0 to 4, and when t5 and t6 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,
a2 is the number of repetitions of the unit in the parentheses, and is an integer from 1 to 1,000.
The definitions of other substituents are the same as those in Chemical Formula 2. A polymer separation membrane comprising the polymer according to any one of claims 1 to 6. anode; cathode; and a polymer separator according to claim 7 provided between the anode and the cathode. A membrane electrode assembly according to at least two claims 8;
A stack including a bipolar plate provided between the membrane electrode assemblies;
A fuel supply unit that supplies fuel to the stack; and
A polymer electrolyte fuel cell comprising an oxidizing agent supply unit that supplies an oxidizing agent to the stack. An anode cell containing an anode and an anode electrolyte;
A cathode cell containing a cathode and a cathode electrolyte; and
A redox flow battery comprising the polymer separator according to claim 7 provided between the anode cell and the cathode cell.