KR101947605B1 - Halogenated compound, polymer and polymer electrolyte membrane using the same - Google Patents

Abstract

The present invention relates to a polymer and a polymer electrolyte membrane including the same, a membrane-electrode assembly including the polymer electrolyte membrane, a fuel cell including the membrane electrode assembly, and a redox flow cell including the polymer electrolyte membrane.

Description

TECHNICAL FIELD [0001] The present invention relates to a halogenated compound, a polymer, and a polymer electrolyte membrane containing the same. BACKGROUND ART [0002]

TECHNICAL FIELD The present invention relates to a halogenated compound, a polymer, and a polymer electrolyte membrane containing the same.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction. The membrane electrode assembly (MEA) of a fuel cell is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane, as a portion where an electrochemical reaction of hydrogen and oxygen takes place.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized and reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active substance directly as electric energy to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).

Fuel cells and redox flow cells are being researched and developed as a next generation energy source because of their high energy efficiency and eco - friendly characteristics with low emission of pollutants.

The most important components of the fuel cell and the redox flow cell are cation exchange polymer electrolyte membranes, which are: 1) excellent proton conductivity 2) cross-over of the electrolyte 3) strong chemical resistance 4) mechanical Physical properties and / or 4) low swelling ratio. The polymer electrolyte membrane is classified into a fluorine system, a partial fluorine system, and a hydrocarbon system. In the case of a partially fluorinated polymer electrolyte membrane, the polymer electrolyte membrane has an excellent physical and chemical stability and a high thermal stability due to its fluorine main chain. Also, like the fluorinated polymer electrolyte membrane, the partial fluorinated polymer electrolyte membrane has the advantages of the hydrocarbon-based polymer electrolyte membrane and the fluorinated polymer electrolyte membrane because the cation-transfer functional group is attached to the end of the fluorinated chain.

However, the partial fluorine-based polymer electrolyte membrane has a problem that the cation transfer function is relatively low because the fine phase separation of the cation-transfer functional groups and the control of aggregation phenomenon are not effectively performed. Therefore, studies have been made to secure a high cation conductivity by controlling the distribution of sulfonic acid groups and the separation of fine phases.

Korean Laid-Open Publication No. 2003-0076057

The present specification is intended to provide a halogenated compound, a polymer, and a polymer electrolyte membrane containing the same.

The present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L is S or SO ₂ ,

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 of 2 to 6,

M is a Group 1 element,

R 1 to R 4 are the same or different and are each independently a halogen group,

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

The present specification also provides a polymer comprising units derived from the above formula (1).

The present invention provides a polymer electrolyte membrane comprising the polymer.

Also, the present disclosure relates to an anode; Cathode; And the above-described polymer electrolyte membrane provided between the anode and the cathode.

The present disclosure includes two or more of the above-described membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.

Finally, the present specification discloses a positive electrode comprising a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane provided between the anode cell and the cathode cell.

The polymer electrolyte membrane comprising a polymer according to one embodiment of the present disclosure easily forms a hydrophilic-hydrophobic phase-separation structure.

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

In addition, the polymer electrolyte membrane is excellent in proton conductivity. As a result, the performance of the fuel cell and / or the redox flow battery including the same is improved.

1 is a schematic view showing an electricity generation principle of a fuel cell.
2 is a schematic view showing an embodiment of a redox flow battery.
3 is a schematic view showing one embodiment of a fuel cell.

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

Whenever a component is referred to as " comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

The present invention provides a compound represented by the above formula (1).

In one embodiment of the present invention, the halogenated compound can be used as a monomer in a polymer. In this specification, S atom or SO ₂ is used as a linker of the - [CR 3 _R 4] _n -A structure of the above formula (1) and the benzene ring. In this case, due to the electron withdrawing character of - [CR 3 _R 4] _n -A connected by S atom or SO ₂ , it is possible to provide a polymer which is easy and stable in the formation of the polymer. The definitions of R3, R4, n and A are the same as described above.

According to one embodiment of the present invention, when SO ₂ is used as the linker of the - [CR 3 _R 4] _n -A structure of the formula (1) and the benzene ring, production of a polymer may be difficult due to stability problems, S linker may be first formed and then an SO ₂ linker polymer may be prepared using an oxidation process.

In one embodiment of the present disclosure, in the case of - [CR 3 R 4] _n -A in formula 1, when R 1 and R 2 are located 3 or 5 of the benzene ring, - [CR 3 R 4] _n -A and R 1 and R 2 are structurally So that the polymeric reaction of the polymer is less affected by the steric hinderance, so that the reactivity can be improved. Therefore, a polymer having a relatively high molecular weight can be polymerized from the compound according to one embodiment of the present specification, and the performance of the polymer film including the polymer can be expected to be improved.

In one embodiment of the present specification, R 1 and R 2 are the same or different from each other and each independently represents a halogen group. Specifically, R 1 and R 2 are each independently F; Cl; Br; And < RTI ID = 0.0 > I. < / RTI >

In another embodiment, R 3 and R 4 are the same or different and are each independently a halogen group. Specifically, R 3 and R 4 are each independently F; Cl; Br; And < RTI ID = 0.0 > I. < / RTI >

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

Monomers comprising units of formula (1) according to one embodiment of the present disclosure can control the number of n. In this case, the length of the structure in the parentheses can be adjusted or the mass of the polymer can be controlled.

Within the range of n, the phase separation of the polymer is easy, and the ion conductivity can be improved.

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

In another embodiment, n is three.

In another embodiment, n is four.

In another embodiment, n is 5.

In another embodiment, n is six.

In another embodiment, n is 7.

In one embodiment of the present disclosure, n is eight.

In another embodiment, n is 9.

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

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

In yet one embodiment, the A is an -SO ₃ H.

In one embodiment of the present disclosure, A is a _{-O (CF 2) m SO 3} H.

In one embodiment of the present disclosure, m is 2.

In another embodiment, m is 3.

In another embodiment, m is 4.

In one embodiment of the present disclosure, m is 5.

In one implementation, m is six.

As described above, A is -SO ₃ H, -SO ₃ of the formula ^{1 - M +, -O (CF} 2) m SO 3 H or _{-O (CF 2) m SO 3} - M + Ann Wu, chemically stable A polymer can be formed.

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

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

In one embodiment of the present specification, the sum of n and m may be preferably 2 to 10.

In one embodiment of the present invention, the compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-21, but is not limited thereto.

 [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

 [Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

.

.

Also provided herein are polymers comprising units derived from the compounds described above.

The term "derived" as used herein means that the bond of the compound is broken or a new bond is formed as the substituent is released, and the unit derived from the compound may mean a repeating unit constituting the polymer. The unit may be included in the main chain in the polymer to constitute the polymer.

Specifically, according to one embodiment of the present invention, the halogenated compound may form a repeating unit while R1 and R2 at positions 3 and 5 of the phenyl group are decreased.

Specifically, the polymer according to one embodiment of the present specification may include a unit derived from a compound represented by the following formula (1).

The unit derived from the compound represented by the formula (1) may be represented by the following formula (1-A).

[Chemical Formula 1-A]

In the above formula (1-A), L, R3, R4, n and A are the same as described above.

In the case where the polymer containing the unit represented by the formula (1) is included in the polymer electrolyte membrane, when R3 and R4 in the general formula (1) are halogen groups, the acidity of A connected to -CR3R4- is increased, The ion conductivity can be improved, and the structure of the polymer electrolyte membrane can be strengthened.

Specifically, according to one embodiment of the present disclosure, when R3 and R4 are fluorine, the advantage can be maximized.

Monomers comprising units of formula (I-A) according to one embodiment of the present disclosure can control the number of n. In this case, the length of the structure in the parentheses can be adjusted to facilitate the phase separation of the polymer electrolyte membrane, and the hydrogen ion migration of the polymer electrolyte membrane can be facilitated. Within the range of n, the phase separation of the polymer is easy, and the ion conductivity can be improved.

In one embodiment of the present invention, the polymer comprises 1 mol% to 100 mol% of the unit represented by the formula (1). Specifically, in one embodiment of the present specification, the polymer includes only the unit represented by the above formula (1). In another embodiment, the polymer may further comprise additional units other than the unit represented by the formula (1). In one embodiment of the present invention, when the polymer further comprises an additional unit, the content of the unit represented by the general formula (1) is preferably 5 mol% to 65 mol%.

The unit represented by the formula (1) according to one embodiment of the present invention plays a role in regulating the ionic conductivity of the separation membrane.

The additional unit according to yet another embodiment may be selected from units that improve the mechanical strength of the polymer, and the unit is not limited as long as it can improve the mechanical strength.

In one embodiment of the present invention, the unit represented by the formula (1-A) and the additional unit may constitute a random polymer.

In this case, the polymer having the unit represented by the formula (1-A) has the structure of - [CR 3 _R 4] _n -A in the formula in the form of a pendant form, Can be easily formed. Therefore, the effect of improving the ionic conductivity of the polymer electrolyte membrane can be expected.

A polymer according to one embodiment of the present disclosure comprises a hydrophilic block and a hydrophobic block, wherein the hydrophilic block is a block polymer comprising units derived from the compounds described above.

In one embodiment of the present disclosure, in the block polymer, the hydrophilic block and the hydrophobic block are contained in a ratio of 1: 0.1 to 1:10. In one embodiment of the present disclosure, the hydrophilic block and the hydrophobic block are contained in the block polymer in a ratio of 1: 0.1 to 1: 2. In another embodiment, in the block polymer, the hydrophilic block and the hydrophobic block are contained in a ratio of 1: 0.8 to 1: 1.2. In this case, the ion transfer ability of the block polymer can be increased.

In one embodiment of the present invention, in the hydrophilic block, the unit represented by the formula (1-A) is contained in an amount of 0.01 mol% to 100 mol% based on the hydrophilic block.

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

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

According to the embodiment of the present invention, in the case of a block polymer, separation of the hydrophilic block and the hydrophobic block is clearly distinguished, so that phase separation is easy and ion transfer can be facilitated. According to one embodiment of the present invention, when the unit represented by the above formula (1-A) is contained, the distinction between the hydrophilic block and the hydrophobic block becomes more clear, and the ion transfer effect can be superior to that of the conventional polymer.

The block polymer means a polymer composed of one block and one or more blocks different from the block connected to each other through a main chain of the polymer.

In one embodiment of the present disclosure, the block polymer may comprise a hydrophilic block and a hydrophobic block. Specifically, in one embodiment, the block polymer may include a hydrophilic block and a hydrophobic block including the unit represented by the formula (1-A).

As used herein, the term " 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 + , and -PO ₃ ^2- 2M ⁺ the group consisting of Or the like. Here, M may be a metallic element. That is, the functional group may be hydrophilic.

The above-mentioned " block having an ion-exchange group " means a block represented by the number of ion-exchange groups per one structural unit constituting the block and an average of at least 0.5 or more blocks per one structural unit. It is more desirable to have an exchange.

As used herein, the term " hydrophobic block " means the polymer block having substantially no ion exchanger.

The above-mentioned " block having substantially no ion-exchanger " means a block having an average of less than 0.1 in terms of the number of ion-exchange groups per structural unit constituting the block, more preferably 0.05 or less, It is more preferable that the block has no ion exchanger.

In one embodiment of the present invention, one or more of the units represented by the following formulas (2-1) to (2-3) may be selected as the additional unit.

Specifically, in one embodiment of the present specification, the polymer further comprises one or two or more units selected from the units represented by formulas (2-1) to (2-3).

[Formula 2-1]

 [Formula 2-2]

[Formula 2-3]

In formulas (2-1) to (2-3)

L 'is a direct bond; CR7R8; C = O; O; S; SO ₂ ; SiR9R10; Or substituted or unsubstituted fluorenylene,

R 7 to R 10 are the same as or different from each other, and each independently hydrogen; An alkyl group; Haloalkyl; Or a phenyl group,

T1 to T4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group,

x, x 'and y are each an integer of 1 to 4,

z is an integer of 1 to 6,

m 'is an integer of 0 to 5,

When x, x ', y, z, and m' are an integer of 2 or more, the structures in parentheses of two or more are the same or different from each other.

In one embodiment of the present invention, X2 and X3 may be the same or different and independently selected from the following structures, but are not limited thereto.

.

.

In the above structure, A 1 and A 2 are the same or different and each independently a monovalent organic group.

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

In the present specification, in the case of the polymer further comprising the branche, the branche can constitute the main chain of the direct polymer, and the mechanical integrity of the thin film can be improved. For example, the branched polymers of the present invention can be prepared by polymerizing a branched hydrophilic block comprising a branched hydrophobic block that does not contain acid substituents and an acid substituent, Without branching the cross-linking of the sulfonated polymer or post-sulfonation, the brancher directly forms the main chain of the polymer and maintains the mechanical integrity of the thin film Hydrophilic blocks that impart ionic conductivity to the minority block and the thin film can be alternately led to chemical bonding.

In one embodiment of the present invention, the polymer further comprises a branche derived from a compound of the following formula (4) or a branche represented by the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)

X is S; O; CO; SO; SO ₂ ; NR; A hydrocarbon-based or fluorine-

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

l is an integer from 0 to 100,

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

Y1 and Y2 are the same or different from each other and each independently represents an aromatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; Or an aliphatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group,

Z is a trivalent organic group.

Illustrative examples of such substituents are described below, but are not limited thereto.

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

Quot; means bonding to the adjacent substituent or the backbone of the polymer.

In the present specification, the branche derived from the compound of formula (4) is an aromatic ring substituted with a halogen group of each of Y1 and Y2; Or a halogen group of an aliphatic ring substituted by a halogen group may act as a branching agent while being separated from an aromatic ring or an aliphatic ring.

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

In the present specification, the term "hydrocarbon-based" means an organic compound consisting solely of carbon and hydrogen, and includes, but is not limited to, straight chain, branched chain, and cyclic hydrocarbon. It may also include, but is not limited to, a single bond, a double bond or a triple bond.

In the present specification, the fluorine-based conjugate means that the carbon-hydrogen bond in the hydrocarbon system is partially or wholly substituted with fluorine.

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

Specific examples of the aromatic hydrocarbon ring include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group and terphenyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, , A fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthene group, and the like, but are not limited thereto.

As used herein, the aromatic heterocycle means a structure containing at least one heteroatom such as O, S, N, Se, etc. instead of a carbon atom in the aromatic hydrocarbon ring. Specific examples include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, an isoquinoline group, an indole group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, A benzothiazole group, a benzothiophene group, a benzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoxazolyl group, a benzothiazolyl group, a benzothiazolyl group, , An oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but the present invention is not limited thereto.

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

Examples of the organic group in the present specification include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the present specification, a trivalent organic group means a trivalent organic group having three bonding sites.

The organic group may form a cyclic structure, may form a cyclic structure, and may form a bond including a heteroatom unless the effect of the invention is impaired.

Specifically, a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-A) -: A represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

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

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

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

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

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

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

In another embodiment, X is a haloalkyl group.

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

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

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

In another embodiment, Y1 and Y2 are each a fluorine-substituted phenyl group. Specific examples thereof include 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl, and the like.

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

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

According to one embodiment of the present invention, Z in formula (5) may be represented by any one of the following formulas (5-1) to (5-3).

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In Formulas 5-1 to 5-3,

L1 To L < 4 > are the same or different and are each independently a direct bond; -S-; -O-; -CO-; Or -SO ₂ - and,

R 1 to R 7 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

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

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

When a, b, c, d, e, f and g are each an integer of 2 or more, the structures in parentheses of 2 or more are the same or different.

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

In yet one embodiment, the L1 is SO _2.

In another embodiment, L1 is S.

In another embodiment, L2 is CO.

In yet one embodiment, the L2 is SO _2.

In yet another embodiment, L2 is S.

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

In yet one embodiment, the L3 is SO _2.

In another embodiment, L3 is S.

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

In yet one embodiment, the L4 is SO _2.

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

In another embodiment, L6 is a direct bond.

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

In one embodiment of the present specification, R1 to R11 are hydrogen.

In one embodiment of the present specification, R7 is a halogen group.

In another embodiment, R7 is fluorine.

Further, in one embodiment of the present invention, the branching agent represented by Formula 5 may be represented by any one of the following structures.

,

,

,

,

,

,

,.

,

,

,

,

,

,

,.

In one embodiment of the present disclosure, the weight average molecular weight of the polymer is from 500 g / mol to 5,000,000 g / mol. In another embodiment of the present disclosure, the weight average molecular weight of the polymer is from 10,000 g / mol to 3,000,000 g / mol. When the weight average molecular weight of the polymer is in the above range, the mechanical properties of the electrolyte membrane containing the polymer are not lowered, the solubility of the appropriate polymer is maintained, and the electrolyte membrane can be easily produced.

The present specification also provides a polymer electrolyte membrane comprising the above-mentioned polymer.

When a polymer containing units derived from the compound according to one embodiment of the present invention is included, it has high mechanical strength and high ion conductivity and can facilitate the phase separation of the electrolyte membrane.

As used herein, the term " electrolyte membrane " is a membrane capable of ion exchange, and includes a membrane, an ion exchange membrane, an ion transport membrane, an ion conductive membrane, a membrane, an ion exchange membrane, A transfer electrolyte membrane, an ion conductive electrolyte membrane, and the like.

The polymer electrolyte membrane according to one embodiment of the present disclosure can be manufactured using materials and / or methods known in the art, except that the polymer electrolyte membrane contains a polymer containing units derived from the above compound.

According to one embodiment of the present invention, the ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less. In another embodiment, the ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.3 S / cm or less.

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

In one embodiment of the present invention, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5.0 mmol / g. When the ion exchange capacity value is in the range, the ion channel in the polymer electrolyte membrane is formed, and the polymer can exhibit ion conductivity.

In one embodiment of the present invention, the thickness of the polymer electrolyte membrane is 1 탆 to 500 탆. The polymer electrolyte membrane having the above-described range of thickness can reduce electric short and cross-over of the electrolyte material and exhibit excellent cation conductivity.

The disclosure also includes an anode; Cathode; And the above-described polymer electrolyte membrane provided between the anode and the cathode.

The membrane-electrode assembly (MEA) means a junction body of an electrode (cathode and anode) where an electrochemical catalytic reaction of fuel and air takes place and a polymer membrane in which hydrogen ions are transferred, and the electrode (cathode and anode) It is a single integral unit.

The membrane-electrode assembly of the present invention can be produced by a conventional method known in the art, such that the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane. For example, the cathode; Anode; And an electrolyte membrane positioned between the cathode and the anode in close contact with each other at 100 to 400 ° C.

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

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

FIG. 1 schematically shows an electricity generating principle of a fuel cell. In a fuel cell, a basic unit for generating electricity is a membrane electrode assembly (MEA), which includes an electrolyte membrane 100 and an electrolyte membrane 100, And an anode 200a and a cathode 200b electrodes formed on both sides of the cathode 200a. 1 showing the principle of electricity generation of a fuel cell, in the anode 200a, oxidation reaction of hydrogen such as hydrogen or hydrocarbons such as methanol and butane occurs, hydrogen ions (H +) and electrons (e-) are generated, The hydrogen ions move through the electrolyte membrane 100 to the cathode 200b. In the cathode 200b, hydrogen ions transferred through the electrolyte membrane 100 react with an oxidizing agent such as oxygen and electrons to generate water. This reaction causes electrons to migrate to the external circuit.

The catalyst layer of the anode electrode is preferably a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum- Lt; / RTI > 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 not only by themselves but also by being 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 ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. The method of coating 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 consist of a catalyst, a polymer ionomer and a solvent.

The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material. As the conductive substrate, carbon paper, carbon cloth or carbon felt can be preferably used. The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive base. The microporous layer can be used to improve the performance of the fuel cell under low humidification conditions and serves to reduce the amount of water flowing out of the gas diffusion layer to make the electrolyte membrane sufficiently wet.

One embodiment of the present disclosure includes at least two membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction.

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

The fuel cell of the present invention comprises a stack, a fuel supply, and an oxidant supply.

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

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

The oxidant supply part 70 serves to supply the oxidant to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected into the pump 70 and used.

The fuel supply unit 80 serves to supply the fuel to the stack 60 and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 Lt; / RTI > 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.

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

In addition, one embodiment of the present disclosure includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane according to an embodiment of the present invention provided between the anode cell and the cathode cell.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized and reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active substance directly as electric energy to be. The redox flow battery utilizes the principle of charging and discharging electrons by receiving electrons when an electrolyte containing an active material having a different oxidation state meets the ion exchange membrane. Generally, a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occur, and a circulation pump circulating the electrolyte between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, Exchange membrane.

When the electrolyte membrane according to one embodiment of the present invention is used as the ion exchange membrane of the redox flow cell, the above-described effect can be obtained.

The redox flow cell of the present specification can be produced according to a conventional method known in the art, except that it includes a polymer electrolyte membrane according to one embodiment of the present specification.

2, the redox flow battery is divided into a positive electrode cell 32 and a negative electrode cell 33 by an electrolyte film 31. As shown in FIG. The anode cell 32 and the cathode cell 33 each include an anode and a cathode. 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 electrolytic solution is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions is changed occurs, thereby charging and discharging occur in the anode and the cathode.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

PREPARATION EXAMPLE 1 Synthesis of Random Polymer

Each of the monomers and K ₂ CO ₃ (molar ratio 4) were mixed at a ratio of 30 wt% of NMP and 30 wt% of benzene and polymerized at 140 ° C. for 4 hours and at 180 ° C. for 16 hours.

The following Examples are the results of preparing a separation membrane using the polymer obtained in Preparation Example 1 and measuring the molecular weight by GPC.

≪ Example 1 >

A polymer was prepared by the method of Production Example 1, and a partial fluorine-containing membrane was prepared, and its molecular weight was measured by GPC, and it is shown in Table 1 below.

Mn (g / mol) Mw (g / mol) Mw / Mn Example 1 40,000 109,000 2.74

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

Claims (17)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
L is S,
A is -SO ₃ H or -O (CF ₂ ) _m SO ₃ H,
m is an integer of 2 to 6,
R 1 to R 4 are the same or different and are each independently a halogen group,
n is an integer of 2 to 10, and structures in 2 to 10 parentheses are the same or different from each other. The method according to claim 1,
Wherein the compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-21).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

. A polymer comprising a unit derived from the compound of claim 1 or 2. The method of claim 3,
Wherein the polymer further comprises a unit represented by the following formula (2-1): < EMI ID =
[Formula 2-1]

In formula (2-1)
L 'is a direct bond; CR7R8; C = O; O; S; SO ₂ ; SiR9R10; Or substituted or unsubstituted fluorenylene,
R 7 to R 10 are the same as or different from each other, and each independently hydrogen; An alkyl group; Haloalkyl; Or a phenyl group,
T1 and T2 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
x and x 'are each an integer of 1 to 4,
When x and x 'are an integer of 2 or more, the structures in parentheses of 2 or more are the same or different from each other. The method of claim 3,
Wherein the polymer is a random polymer. The method of claim 3,
Wherein the polymer comprises a hydrophilic block and a hydrophobic block,
Wherein the hydrophilic block is a block polymer comprising units derived from the compound. The method of claim 6,
Wherein the hydrophilic block and the hydrophobic block are contained in the block polymer in a ratio of 1: 0.1 to 1:10. The method of claim 3,
Wherein the polymer further comprises a branche derived from a compound of formula (4) or a branche represented by formula (5): < EMI ID =
[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)
X is S; O; CO; SO; SO ₂ ; NR; A hydrocarbon-based or fluorine-
R is an aromatic ring substituted with a halogen group; Or an aliphatic ring substituted with a halogen group,
l is an integer from 0 to 100,
When l is 2 or more, two or more X's are the same as or different from each other,
Y1 and Y2 are the same or different from each other and each independently represents an aromatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; Or an aliphatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group,
Z is a trivalent organic group. The method of claim 8,
Wherein the branche represented by the general formula (5) is any one of the following structures:

,

,

,

,

,

,

. The method of claim 3,
Wherein the weight average molecular weight of the polymer is from 500 g / mol to 5,000,000 g / mol. A polymer electrolyte membrane comprising the polymer of claim 3. The method of claim 11,
The ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm to 0.5 S / cm / RTI > The method of claim 11,
Wherein the polymer electrolyte membrane has an ion exchange capacity (IEC) value of 0.01 mmol / g to 5 mmol / g. The method of claim 11,
Wherein the polymer electrolyte membrane has a thickness of 1 占 퐉 to 500 占 퐉. Anode; Cathode; And a polymer electrolyte membrane according to claim 11 provided between the anode and the cathode. At least two membrane-electrode assemblies according to claim 15;
A stack including a bipolar plate disposed between the membrane-electrode assemblies;
A fuel supply unit for supplying fuel to the stack; And
And an oxidant supplier for supplying the oxidant to the stack. A positive electrode including a positive electrode and a positive electrode electrolyte;
A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And
The redox flow battery according to claim 11, which is provided between the positive electrode cell and the negative electrode cell.

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