KR20200069660A - Polymer, polymer separation membrane using same, membrane electrode assembly, fuel cell and redox flow cell using same - Google Patents

Abstract

The present specification relates to a polymer comprising hydrophilic and hydrophobic blocks, wherein the hydrophilic block includes a unit represented by chemical formula 1, and the hydrophobic block includes a unit represented by chemical formula 2, a polymer separation membrane comprising the same, and a membrane electrode assembly, a fuel cell and a redox flow battery comprising the same. The polymer according to one embodiment of the present specification enables simplification of a process, thereby being economical.

Description

Polymer, polymer separation membrane containing the same, membrane electrode assembly including the same, fuel cell, and redox flow battery TECHNICAL FIELD

The present specification relates to a polymer, a polymer separator comprising the same, a membrane electrode assembly comprising the same, a fuel cell and a redox flow cell.

The separator material for fuel cells has a high ionic conductivity, and at the same time, to prevent the decrease in cell efficiency when driving 1) prevent crossover of electrolyte materials, 2) strong chemical resistance when operating cells, 3) strengthen mechanical properties, 4 ) It should have characteristics such as low swelling ratio. Currently, most of the separators of fuel cells use Nafion. Nafion has high ionic conductivity and good thermal and mechanical properties, but has the disadvantage of increasing the film resistance when increasing the thickness to ensure high price, methanol crossover, and mechanical properties. Therefore, it is necessary to develop a material having high ionic conductivity of Nafion and mechanical properties of hydrocarbons at the same time.

United States Patent Application Publication No. 2008-0241626

An object of the present invention is to provide a polymer, a polymer separation membrane comprising the same, a membrane electrode assembly comprising the same, a fuel cell and a redox flow battery.

One embodiment of the present specification includes a hydrophilic block and a hydrophobic block, the hydrophilic block includes a unit represented by Formula 1, and the hydrophobic block provides a polymer comprising a unit represented by Formula 2 below do.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

L1 is a direct bond; -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 + , and

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 as or different from each other, and each independently a halogen group,

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

X1 is -SO ₂ -; Or ―CO―,

T1 and T2 are the same as or different from each other, and 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,

는 인접한 치환기 또는 중합체의 주쇄와 결합하는 것을 의미한다.

Means to bond with an adjacent substituent or the main chain of the polymer.

In addition, an exemplary embodiment of the present specification provides a polymer separator comprising the above-described polymer.

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

In addition, another exemplary embodiment of the present specification is two or more of the above-described membrane electrode assembly; A stack including 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 oxidizing agent supply unit for supplying an oxidizing agent to the stack.

Finally, another exemplary embodiment of the present specification includes an anode cell including an anode and an anode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And it provides a redox flow battery comprising a polymer separation membrane of one embodiment described above provided between the anode cell and the cathode cell.

The polymer according to the exemplary embodiment of the present specification is economical because it is possible to simplify the process since no post-treatment process for purification of the polymer is required after the polymerization reaction.

The polymer separation membrane according to the exemplary embodiment of the present specification can achieve high ionic conductivity due to a hydrophilic block containing perfluorosulfonic acid, and lower water uptake due to the hydrophobic block, humidifying conditions In can improve the mechanical stability of the membrane.

1 is a schematic view showing the principle of electricity generation in 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 view showing a ¹ H-NMR spectrum of the polymer prepared according to Example 1.
5 is a view showing the molecular weight distribution of the polymer prepared according to Example 1.
6 is a view showing a ¹ H-NMR spectrum of the polymer prepared according to Example 2.
7 is a view showing the molecular weight distribution of the polymer prepared according to Example 2.
Figure 8 shows the cation conductivity of the prepared polymer separation membrane.

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

In the present specification, when a part is to “include” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification, "derived" means that the bond of the compound is broken, or that a new bond occurs as the substituent is removed, and the 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 in the polymer to constitute the polymer.

In the present specification, "unit" refers to a structure in which a monomer is included in a polymer and repeated, and a structure in which the monomer is bonded to the polymer by polymerization.

In the present specification, the meaning of “comprising units” means being included in the main chain in the polymer.

In the present specification, "separation membrane" is a membrane capable of exchanging ions, such as membranes, ion exchange membranes, ion transfer membranes, ion conducting membranes, ion exchange membranes, ion transfer membranes, ion conducting membranes, ion exchange electrolyte membranes, ion transfer membranes Electrolyte membranes, or ion conductive electrolyte membranes.

In one embodiment of the present invention, the polymer comprises a hydrophilic block and a hydrophobic block, the hydrophilic block includes a unit represented by Formula 1, and the hydrophobic block includes a unit represented by Formula 2 below. Provides

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

L1 is a direct bond; -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 + , and

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 as or different from each other, and each independently a halogen group,

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

X1 is -SO ₂ -; Or ―CO―,

T1 and T2 are the same as or different from each other, and 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,

는 인접한 치환기 또는 중합체의 주쇄와 결합하는 것을 의미한다.

Means to bond with an adjacent substituent or the main chain of the polymer.

Since the polymer of the present specification does not require a post-treatment process for purification of the polymer, it is possible to simplify the process and is economical in terms of cost.

In addition, the polymer prepared by the production method according to an exemplary embodiment of the present specification transmits ions through a hydrophilic block, and secures mechanical properties through a hydrophobic block, while sulfuric acid generally introduced into hydrocarbon-based polymers (- SO ₃ H) can be imparted with high ionic conductivity through the introduction of perfluorosulfonic acid (ex, -CF ₂ CF ₂ SO ₃ H), which is super acid.

In general, for the synthesis of a polymer containing perfluorosulfonic acid, a method of synthesizing a polymer having a halogen element (ex, Br, I) on the main chain or a side of the polymer and using a catalytic reaction using Cu or Pd is used. . In this case, two or more reaction steps are required for polymer polymerization and functional group introduction, and an additional process for removing the metal catalyst used in the catalytic reaction is required. In addition, more than equivalent chemicals are required to introduce perfluorsulfonic acid. However, there is an advantage in that the simplification of the reaction process is possible when using a monomer in which perfluorosulfonic acid is introduced as in one embodiment of the present specification.

The unit represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has high reactivity in the polymerization process, and may increase process efficiency. In addition, the polymer separation membrane prepared using the unit can easily form a hydrophilic-hydrophobic phase separation structure. In addition, the polymer separation membrane comprising the 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 separation membrane containing the unit has excellent ion conductivity. In addition, the units are thermally and chemically stable.

In this specification, the term "substituted or unsubstituted" is deuterium; Halogen group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heteroaryl group, or one or more substituents selected from the group consisting of, or substituted with two or more substituents among the exemplified substituents, or having no substituents. For example, "substituents 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 Heteroaryl group, a heteroaryl group substituted with a heteroaryl group, but is not limited thereto.

In the present specification, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited if the position at which the hydrogen atom is substituted, that is, the substituent is substitutable, 2 In the case of abnormal substitution, two or more substituents may be the same or different from each other.

In this specification, "hydrophilic block" means 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 +, -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 M ⁺ may be, and -O (CF _{2) w} PO _3, at least one selected from the group consisting of _{^{2- 2M + -) w PO 3}} H 2, -O (CF 2) w PO 3 H. Here, M is a group 1 element, and w may have a range of 1<w<10. That is, the functional group can be hydrophilic.

In the present specification, "block having an ion exchange group" means a block represented by the number of ion exchange groups per one structural monomer constituting the block, and an average of 0.5 or more, and an average of 1.0 or more per structural monomer. It is more preferable to have an ion exchange group.

As used herein, "hydrophobic block" refers to the polymer block that is substantially free of ion exchange groups.

In the present specification, "a block having substantially no ion-exchange group" 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. , It is more preferable if it is a block having no ion exchange groups.

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

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 20. According to an exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, 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 an exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but may be 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 carbon number of the aryl group is 6 to 20. The monocyclic aryl group may be 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, and the like, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms include one or more atoms selected from the group consisting of N, P, O, S, and Si. Can be. The number of carbon atoms is not particularly limited, and preferably has 2 to 30 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms in the heteroaryl group is 2 to 20 carbon atoms. The heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, isooxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Triazinyl group, triazolyl group, acridil group, pyridazinyl group, pyrazinyl group, and the like, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of 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, and the like, but is not limited thereto.

According to one embodiment of the present specification, the hydrophilic block may include a unit represented by Chemical 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 a m ^+, or _{-O (CF 2) m PO 3} 2- 2M + -) m PO 3 H 2, -O (CF 2) m PO 3 H.

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

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

According to one 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 ⁺ , The polymer containing the unit represented by the formula (1) can be formed to be chemically stable.

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 one embodiment of the present specification, R2 and R3 are the same as or different from each other, and each independently a halogen group.

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

According to an exemplary embodiment of the present specification, k is an integer of 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 of 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, structures in parentheses are the same or different from each other.

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

According to an exemplary embodiment of the present specification, the unit of formula 1 may be derived from the following formula 1A.

[Formula 1A]

In Formula 1A,

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

The definition of other substituents is the same as Formula 1.

According to an exemplary embodiment of the present specification, at least two of the R5 to R9 is a halogen group.

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

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

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

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

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

According to the 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, the 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 the 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, the T1 and T2 are the same as or different from each other, and 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.

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

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

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

[Formula 2A]

In Chemical Formula 2A,

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

The definition of other substituents is the same as Formula 2.

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

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

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

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

[Formula B1]

In the above formula B1,

X2 is a direct bond; ―O―; Or ―S―,

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

T3 and T4 are the same as or different from each other, and 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.

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, the Z3 And Z4 is a hydroxyl group.

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

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

In the present specification, the hydrophilic block provides a polymer that further includes a repeating unit represented by Chemical Formula 3 below.

[Formula 3]

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

T3 and T4 are the same as or different from each other, and 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 repeating number of units in parentheses, and is an integer from 1 to 1,000.

The definition of other substituents is the same as that of formula (1).

According to one embodiment of the present specification, X2 to X4 are a direct bond.

According to one embodiment of the present specification, X2 to X4 are the same as or different from each other, and each independently ———; Or ―S―.

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

According to an exemplary 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 is -O.

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

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

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

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

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

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

[Formula B2]

In the above formula B2,

X5 is a direct bond; ―O―; Or ―S―,

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

T5 and T6 are the same as or different from each other, and 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 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 is a hydroxyl group.

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

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

In the present specification, the hydrophobic block provides a polymer that further includes a repeating unit represented by Chemical Formula 4 below.

[Formula 4]

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

T5 and T6 are the same as or different from each other, and 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 parentheses are the same or different from each other,

a2 is the repeating number of units in 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, the X5 to X7 is a direct bond.

According to one embodiment of the present specification, X5 to X7 are the same as or different from each other, and each independently ———; Or ―S―.

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

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

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

According to an exemplary embodiment of the present specification, the formula 4 may be represented by the following formulas 4-1 to 4-4.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

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

는 인접한 치환기 또는 중합체의 주쇄와 결합하는 것을 의미한다.According to an exemplary embodiment of the present specification,

Means to bond with an adjacent substituent or the main chain of the polymer.

According to one embodiment of the present specification, the polymer may be a random polymer including 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 the present specification, "brancher (Brancher)" serves to link or crosslink the polymer chain.

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

According to the exemplary embodiment of the present specification, in the case of the polymer further comprising the brancher, the brancher can directly constitute the main chain of the polymer, and improve the mechanical density of the thin film. For example, a branched polymer according to one 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 this, the branch chain directly constitutes the main chain of the polymer, and the mechanical structure of the thin film is performed without performing post-treatment sulfonation or cross-linking of the sulfonated polymer. The hydrophobic block that maintains the degree of integration and the hydrophilic block that imparts ion conductivity to the thin film may alternately lead to chemical bonding.

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

[Formula 5]

In Chemical Formula 5,

Z is a trivalent organic group.

In this specification, an "organic group" includes an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. Further, the organic group may be either linear, branched or cyclic.

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

In addition, according to an exemplary embodiment of the present specification, the organic group may form a cyclic structure, and may form a bond including a hetero atom unless the effect of the invention is impaired. Specifically, bonds containing heteroatoms, such as an oxygen atom, a nitrogen atom, and a silicon atom, are mentioned. As a specific example, 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 bonds, sulfonyl bonds, sulfinyl bonds, azo bonds, and the like.

In the present specification, the cyclic structure may include the aforementioned 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 hetero ring, and may be monocyclic or polycyclic.

In the present specification, as the aromatic hydrocarbon ring, a monocyclic aromatic ring such as a phenyl group, a biphenyl group, or a terphenyl group and a naphthyl group, a binaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetrasenyl group , A polycyclic aromatic ring such as a chrysenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthene group, and the like. In the present specification, the description of the aryl group may be applied to the aromatic hydrocarbon ring.

In the present specification, an aromatic hetero ring means a structure including one or more atoms selected from the group consisting of hetero atoms such as N, P, O, S, Si, and the like, instead of carbon atoms in the aromatic hydrocarbon ring, wherein The description of the heteroaryl group can be applied. Specifically, thiophene group, furan group, pyrrol 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, isooxazolyl group , A thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

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

In the present specification, the aliphatic hetero ring has a structure including at least one atom selected from the group consisting of hetero atoms such as N, P, O, S, Se, Ge and Si in the aliphatic hydrocarbon ring instead of carbon atoms. it means.

In the present specification, a description of the aromatic hetero ring and the aliphatic hetero ring 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, the formula 5 may be represented by the following 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,

L21 to L27 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -CO-; Or -SO ₂ -,

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

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

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

According to the 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 the 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 the 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 the 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, the W11 to W21 is hydrogen.

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

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

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

According to one 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 a specific embodiment, 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 are not deteriorated, and the solubility of the appropriate polymer is maintained to facilitate the manufacture of 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 a hydrophobic block of the block polymer is a unit represented by Formula 2 It may include.

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 repeating unit represented by Formula 3, and a hydrophobic block of the block polymer is represented by Formula 4 Repeating units.

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

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

Accordingly, the polymer according to an exemplary embodiment of the present specification, by adjusting the ratio of the hydrophilic block and the hydrophobic block, to adjust the ion exchange capacity (Ion Exchange Capacity, IEC) in the membrane electrode assembly, fuel cell, or redox flow cell You can.

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

According to one 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 a specific embodiment, it is 2,000 g/mol to 400,000 g/mol. According to another exemplary embodiment, it is 5,000 g/mol to 400,000 g/mol.

According to one 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 a specific embodiment, it is 2,000 g/mol to 400,000 g/mol. According to another exemplary 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 separation and division of the hydrophilic block and the hydrophobic block are clear, so phase separation is easy, and ion transfer may be easy.

According to the exemplary embodiment of the present specification, when the unit represented by Chemical Formula 1 is included, the distinction between the hydrophilic block and the hydrophobic block becomes more clear, and an ion transfer effect may be superior to that of a conventional polymer.

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

According to one embodiment of the present specification, preparing a first monomer including a unit represented by Chemical Formula 1; Preparing a second monomer including a unit represented by Chemical Formula 2; And polymerizing the first and second monomers.

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

The present specification provides a polymer separator comprising the aforementioned polymer.

According to the exemplary embodiment of the present specification, the polymer separation membrane includes a unit represented by Chemical Formula 1 in a hydrophilic block, and a unit represented by Chemical Formula 2 in a hydrophobic block in the polymer. It can be prepared using materials and/or methods known in the art. For example, it may be performed by applying a solution containing the polymer, and drying and/or curing.

According to the exemplary embodiment of the present specification, the coating may be a method such as a tape casting method, a dip coating method, a spray coating method, a spin coating method, or the like. have.

According to an exemplary embodiment of the present specification, the solvent used in the preparation of the polymer membrane is N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N,N- Dimethylpyrrolidone (N,N-dimethylpyrollidone (NMP)), diphenylsulfone, N,N-dimethylformamide (DMF), etc. may be used, but is not 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 one 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 the exemplary embodiment of the present specification, the method of manufacturing the polymer separator may further include adding an acid solution to a solution containing the polymer. The acid solution may be hydrochloric acid (HCl).

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

According to one 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 12 hours or more, and finally dried at 80°C for a vacuum oven for 12 hours or more. can do.

According to one embodiment of the present specification, the ion conductivity of the polymer separator is 0.001 mS/cm to 8 mS/cm. It is preferably 0.001 mS/cm to 5 mS/cm.

According to one embodiment of the present specification, the cationic conductivity of the polymer separator is 0.001 mS/cm to 8 mS/cm. It is preferably 0.001 mS/cm to 5 mS/cm.

According to an exemplary embodiment of the present specification, the ion conductivity (cationic conductivity) of the polymer separation membrane may be measured by different humidifying conditions. In the present specification, the humidification condition may mean relative humidity (RH) 10% to 100%.

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

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

Ion conductivity (∂) = l/(R x d)

Where l is the distance between the two electrodes (1 cm), 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 in S/cm.

In the present specification, the ion conductivity may mean cationic conductivity.

According to an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer separation membrane is 0.01 mmol / g to 5.0 mmol / g. When the ion exchange capacity value ranges, an ion channel is formed in the polymer separation membrane, and the polymer may exhibit excellent ion conductivity.

According to an exemplary embodiment of the present specification, the thickness of the polymer separation membrane is 1 ㎛ to 500 ㎛. The polymer membrane having a thickness in the above range may reduce electric short and cross over of the electrolyte material, and exhibit excellent cationic conductivity characteristics.

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

In the present specification, "membrane electrode assembly (MEA)" means an electrode (cathode and anode) in which an electrochemical catalytic reaction of fuel and air occurs and a polymer separator in which hydrogen ions are transferred, and an electrode (cathode and cathode) Anode) and a single membrane-bonded unit.

According to an exemplary embodiment of the present specification, the membrane electrode assembly is in a form that the catalyst layer of the anode and the catalyst layer of the cathode contact the polymer separation membrane, it can be prepared according to a conventional method known in the art. In one example, the cathode; Anode; And it may be prepared by heat-pressing to 100 ℃ to 400 ℃ in a state in close contact with the polymer membrane positioned between the cathode and the anode.

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 again 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 again include a cathode microporous layer and a cathode electrode substrate.

FIG. 1 schematically illustrates the principle of electricity generation in a fuel cell. In a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is a separator 100 and both sides of the separator 100 It is composed of an anode (200a) and a cathode (200b) formed on the electrode. Referring to Fig. Showing the electricity generating principle of a fuel cell 1, an anode (200a) in the hydrogen or methanol, up the oxidation reaction of fuel of hydrocarbon such as butane hydrogen ions (H ⁺⁾ and electron (e ^-) is generated and , Hydrogen ions move to the cathode 200b through the separation membrane 100. In the cathode 200b, hydrogen ions transferred through the separator 100 react with oxidizing agents such as oxygen and electrons to generate water. The reaction causes electron movement to occur in 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. Can be used.

The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and a platinum or platinum-transition metal alloy can 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 may be performed by a conventional method known in the art, for example, the catalyst ink may be directly coated on a separator or coated on a gas diffusion layer to form a 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. The catalyst ink may typically be composed of a catalyst, a polymer ionomer, and a solvent.

The gas diffusion layer serves as a current conductor and serves as a passage for the reaction gas and water, and has a porous structure. Therefore, the gas diffusion layer may be formed of 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 can be used to improve the performance of the fuel cell under low-humidity conditions, and serves to keep the polymer membrane in a sufficiently wet state by reducing the amount of water passing out of the gas diffusion layer.

One embodiment of the present specification is two or more of the above-described membrane electrode assembly; A stack including 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 oxidizing agent supply unit for supplying an oxidizing agent to the stack.

A fuel cell is an energy conversion device that directly converts chemical energy of fuel into electrical energy. That is, the fuel cell is a power generation method that uses fuel gas and an oxidizing agent, and generates electricity using electrons generated during the redox reaction.

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

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

3 schematically shows the structure of a fuel cell, and 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 more of the above-described membrane electrode assemblies, and when two or more membrane electrode assemblies are included, includes a separator interposed therebetween. The separator serves to prevent the electrical connection of the membrane electrode assemblies and transfer fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidizing agent supply unit 70 serves to supply the oxidizing agent to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air may be injected by pump.

The fuel supply unit 80 serves to supply fuel to the stack 60, and the fuel tank 81 for storing fuel and the pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60. Can be configured. As the fuel, gas 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 the exemplary embodiment of the present specification, when the polymer separation membrane is used as an ion exchange membrane of a fuel cell, the above-described effect may be exhibited.

In addition, according to one embodiment of the present specification, an anode cell including an anode and a cathode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And it provides a redox flow battery comprising the above-described polymer separator provided between the anode cell and the cathode cell.

Redox flow battery (oxidation-reduction flow battery, Redox Flow Battery) is a system in which the active substance contained in the electrolyte is oxidized, reduced, and charged and discharged, and is an electrochemical storage device that stores the chemical energy of the active substance directly as electric energy. to be. Redox flow batteries use the principle of charging and discharging by exchanging electrons when an electrolyte containing an active material having different oxidation states meets the ion exchange membrane. In general, a redox flow battery is composed of a tank containing an electrolyte, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte between the tank and the battery cell, and the unit cells of the battery cell are electrodes, electrolytes, and ions. Includes an exchange membrane.

According to one embodiment of the present specification, when the polymer separation membrane is used as the ion exchange membrane of the redox flow battery, the above-described effect may be exhibited.

According to the exemplary embodiment of the present specification, the redox flow battery may be manufactured according to a conventional method known in the art, except that the polymer separation membrane is included.

As shown in FIG. 2, the redox flow battery is divided into a positive electrode cell 32 and a negative electrode 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 a 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 (ie, a redox reaction) in which the number of oxidized ions is changed occurs, so that charge and discharge occur at the anode and cathode.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification 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 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 20.000 g (41.64 mmol), 4,4'-Biphenol 9.692 g (52.05 mmol), Sulfone crosslinker 2.436 g (3.12 mmol), nitrogen with 68 mL of N-Methyl-2-pyrrolidone (NMP) and 30 mL of toluene In an atmosphere, reaction was performed using 28.774 g (208.20 mmol) of potassium carbonate as a catalyst. The reaction mixture was stirred for 3 hours in an oil bath at a temperature of 140°C, and water and toluene were removed by reflux distillation. After that, the temperature was raised to 185°C, and reaction was performed for 24 hours.

After the reaction, the temperature was lowered to room temperature, and the synthesized random polymer solution was slowly dropped into 2000 mL HCl Solution (1M) to obtain a precipitate. Only a 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.

Each embodiment was shown in Figures 4 and 5, the ¹ H-NMR spectrum, and molecular weight distribution of the produced polymer in accordance with Example 1.

<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 10.000 g (20.82 mmol), 4,4'-Thiobisbenzenethiol 6.518 g (26.03 mmol), Sulfone crosslinker 1.218 g (1.56 mmol) was added and 47 mL of N-Methyl-2-pyrrolidone (NMP) and 20 mL of toluene were used. In the atmosphere, reaction was performed using 14.387 g (104.10 mmol) of potassium carbonate as a catalyst. The reaction mixture was stirred for 3 hours in an oil bath at a temperature of 140°C, and water and toluene were removed by reflux distillation. After that, the temperature was raised to 185°C, and reaction was performed for 24 hours.

After the reaction, the temperature was lowered to room temperature, and the synthesized random polymer solution was slowly dropped into 2000 mL HCl Solution (1M) to obtain a precipitate. Only a 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.

Each embodiment was shown in Figures 6 and 7. The ¹ H-NMR spectrum, and molecular weight distribution of the produced polymer in accordance with Example 2.

<Preparation of polymer separation membrane>

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

After separating the prepared polymer separation membrane into distilled water, each of the 1M hydrochloric acid (HCl) solution was treated at room temperature for 24 hours and 1M sulfuric acid (H ₂ SO ₄ ) solution was treated at 80°C for 12 hours. After repeated washing with distilled water, it was kept in distilled water for 24 hours.

Subsequently, the polymer separator was taken out from distilled water, and dried in a vacuum oven at 80° C. for 12 hours to prepare a polymer separator. The prepared polymer separator was in the form of a brown transparent film.

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

IEC (calc.)
(meq/g) Cationic conductivity 1
(mS/cm)
@ RH30%,70℃ Cationic conductivity 2
(mS/cm)
@ RH50%,70℃ Cationic conductivity 3
(mS/cm)
@ RH80%,70℃ Cationic 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 the examples, it can be confirmed that it is possible to synthesize a polymer containing perfluorsulfonic acid without reacting with an equivalent of a chemical equivalent or more in order to introduce a post-treatment process for purifying the polymer and perfluorsulfonic acid, which simplifies the reaction process. It means that it is possible.

In addition, through the calculation of the ion exchange capacity and the value of cation conductivity, 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
81: fuel tank
82: Pump

Claims (10)

Hydrophilic block and hydrophobic block,
The hydrophilic block includes a unit represented by Formula 1 below,
The hydrophobic block is a polymer comprising a unit represented by the following formula (2):
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
L1 is a direct bond; -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 + , and
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 as or different from each other, and each independently a halogen group,
n is an integer of 2 to 10, and when n is an integer of 2 or more, structures in parentheses are the same or different from each other,
X1 is -SO ₂ -; Or ―CO―,
T1 and T2 are the same as or different from each other, and 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,

Means to bond with an adjacent substituent or the main chain of the polymer. The method according to claim 1,
The L1 is -S- is a polymer. The method according to claim 1,
M ⁺ is a polymer, m is an integer from 2 to 6, M is a group 1 element ^- and A is _{-O (CF 2) m SO 3} H, or _{-O (CF 2) m SO 3} . The method according to claim 1,
Wherein R2 and R3 are F. The method according to claim 1,
The hydrophilic block is a polymer that further comprises a repeating unit represented by the following Chemical Formula 3:
[Formula 3]

In Chemical Formula 3,
X2 to X4 are the same as or different from each other, and each independently a direct bond; ―O―; Or ―S―,
T3 and T4 are the same as or different from each other, and 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 repeating number of units in parentheses, and is an integer from 1 to 1,000.
The definition of other substituents is the same as that of formula (1). The method according to claim 1,
The hydrophobic block further comprises a repeating unit represented by Formula 4 below:
[Formula 4]

In Chemical Formula 4,
X5 to X7 are the same as or different from each other, and each independently a direct bond; ―O―; Or ―S―,
T5 and T6 are the same as or different from each other, and 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 parentheses are the same or different from each other,
a2 is the repeating number of units in parentheses, and is an integer from 1 to 1,000.
The definition of other substituents is the same as that of formula (2). A polymer separation membrane comprising the polymer according to claim 1. Anode; Cathode; And a polymer separation membrane according to claim 7 provided between the anode and the cathode. A membrane electrode assembly according to claim 8 of 2 or more;
A stack including a bipolar plate provided between the membrane electrode assemblies;
A fuel supply unit supplying fuel to the stack; And
A polymer electrolyte fuel cell including an oxidizing agent supply unit for supplying an oxidizing agent to the stack. An anode cell comprising an anode and an anode electrolyte;
A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And
Redox flow battery comprising a polymer separation membrane according to claim 7 provided between the anode cell and the cathode cell.

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