KR102629899B1 - Compound, polymer comprising monomer derived from same, polymer separation membrane using same, membrane electrode assembly, fuel cell and redox flow cell using same - Google Patents

Abstract

This specification relates to a compound represented by Formula 1 above, a polymer containing units derived therefrom, a polymer separator containing the same, a membrane electrode assembly containing the same, a fuel cell, and a redox flow battery.

Description

Compound, polymer containing units derived therefrom, polymer separator containing this, membrane electrode assembly containing this, fuel cell and redox flow battery {COMPOUND, POLYMER COMPRISING MONOMER DERIVED FROM SAME, POLYMER SEPARATION MEMBRANE USING SAME, MEMBRANE ELECTRODE ASSEMBLY, FUEL CELL AND REDOX FLOW CELL USING SAME}

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

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

US Patent Application Publication No. 2008-0241626

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

An exemplary embodiment of the present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 to L3 are the same or different from each other and are each independently directly bonded; -S-; -O-; ―SO ₂ ―; or -CO-,

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

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

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

R1 to R10 are the same or different from each other, and are each independently hydrogen; halogen group; or a hydroxy group,

At least one of R1 to R5 is a halogen group,

At least one of R6 to R10 is a halogen group,

k is an integer from 0 to 3, and when k is an integer of 2 or more, R is the same or different,

R11 and R12 are the same or different from each other and are each independently a halogen group,

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

One embodiment of the present specification provides a polymer containing units derived from the above-mentioned compounds.

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

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

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

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

A polymer using a compound according to an exemplary embodiment of the present specification has improved solubility, makes it easy to process the polymer, and has excellent stability.

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

In addition, the polymer separator according to an exemplary embodiment of the present specification has a low swelling ratio and can maintain excellent ionic conductivity even under low humidification conditions.

1 is a schematic diagram showing the electricity generation principle of a fuel cell.
Figure 2 is a diagram schematically showing an embodiment of a redox flow battery.
Figure 3 is a diagram schematically showing an embodiment of a fuel cell.
Figures 4 and 5 show ¹ H-NMR spectra of monomers prepared according to Examples 1 and 2.
Figures 6 and 7 show the LC-Mass results of the monomers prepared according to Examples 1 and 2.

Hereinafter, this specification will be described in more detail.

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

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

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

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

In this specification, “separator” refers to a membrane capable of exchanging ions, including a membrane, ion exchange membrane, ion transport membrane, ion conductive membrane, ion exchange separator, ion transport separator, ion conductive separator, ion exchange electrolyte membrane, ion transport. Includes an electrolyte membrane or an ion conductive electrolyte membrane.

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

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

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

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

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

An exemplary embodiment of the present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 to L3 are the same or different from each other and are each independently directly bonded; -S-; -O-; ―SO ₂ ―; or -CO-,

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

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

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

R1 to R10 are the same or different from each other, and are each independently hydrogen; halogen group; or a hydroxy group,

At least one of R1 to R5 is a halogen group,

At least one of R6 to R10 is a halogen group,

k is an integer from 0 to 3, and when k is an integer of 2 or more, R is the same or different,

R11 and R12 are the same or different from each other and are each independently a halogen group,

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

The compounds of this specification can be homopolymerized or copolymerized.

According to an exemplary embodiment of the present specification, L1 to L3 are the same or different from each other and are each independently directly bonded; -S-; -O-; ―SO ₂ ―; Or -CO-.

According to an exemplary embodiment of the present specification, L1 to L3 are the same or different from each other and are each independently directly bonded; -S-; or -SO ₂ -.

According to an exemplary embodiment of the present specification, L1 to L3 are equal to each other.

According to an exemplary embodiment of the present specification, all of L1 to L3 are -S-.

According to an exemplary embodiment of the present specification, all of L1 to L3 are -SO ₂ -.

According to an exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, and are each independently hydrogen; Or it is a halogen group.

According to an exemplary embodiment of the present specification, R is hydrogen.

According to an exemplary embodiment of the present specification, R1 to R10 are the same as or different from each other, and are each independently hydrogen; It is a halogen group, at least one of R1 to R5 is a halogen group, and at least one of R6 to R10 is a halogen group.

According to an exemplary embodiment of the present specification, among R1 to R10, one of R1 to R5 is a halogen group, one of R6 to R10 is a halogen group, and all others are hydrogen.

According to an exemplary embodiment of the present specification, among R1 to R10, one of R1 to R5 is F or Cl, one of R6 to R10 is F or Cl, and all others are hydrogen.

According to an exemplary embodiment of the present specification, among R1 to R10, one of R1 to R5 is F, one of R6 to R10 is F, and all others are hydrogen.

According to an exemplary embodiment of the present specification, among R1 to R10, one of R1 to R5 is Cl, one of R6 to R10 is Cl, and all others are hydrogen.

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

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

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

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

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

According to an exemplary embodiment of the present specification, R11 and R12 are F.

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

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

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

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

X1 and

In an exemplary embodiment of the present specification, X1 and X2 are each independently F or Cl.

In one embodiment of the present specification, X1 and X2 are F.

In one embodiment of the present specification, X1 and X2 are Cl.

According to an exemplary embodiment of the present specification, Formula 1 may be represented by Formula 3 or Formula 4 below.

[Formula 3]

[Formula 4]

In Formulas 3 and 4, n, m, X1, X2, and M are as defined in Formulas 1 and 2.

According to an exemplary embodiment of the present specification, Formula 1 may be expressed as Formula 5 or Formula 6 below.

[Formula 5]

[Formula 6]

In Formulas 5 and 6, M is as defined in Formula 1.

In one embodiment of the present specification, a polymer containing units derived from the above-mentioned compounds can be provided.

In an exemplary embodiment of the present specification, a polymer containing a unit represented by the following formula (7) may be provided.

[Formula 7]

In Formula 7,

means that it can be combined with an adjacent substituent or the main chain of the polymer, and other substituents are as defined in Formula 1.

In an exemplary embodiment of the present specification, the unit represented by Formula 7 may be represented by the following Formulas 8 and 9.

[Formula 8]

[Formula 9]

In Formulas 8 and 9, means that it can bind to an adjacent substituent or the main chain of the polymer, and M is as defined in Formula 1.

Additionally, in one embodiment of the present specification, the polymer may be produced by homopolymerization or copolymerization of the above compound.

In one embodiment of the present specification, the polymer may be polymerized using a metal catalyst. Examples of the metal catalyst include Ni catalyst and Pd catalyst, but are not limited thereto.

In one embodiment of the present specification, the polymer may be polymerized through a nucleophilic substitution reaction using a monomer. Examples of the monomer include dihydroxy monomer and dithiol monomer, but are not limited thereto.

In one embodiment of the present specification, the polymer may be one in which units represented by Formula 8 or Formula 9 are repeated.

In one embodiment of the present specification, the polymer may further include a unit represented by the following formula (10).

[Formula 10]

In Formula 10,

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

means that it can bind to an adjacent substituent or the main chain of the polymer.

In one embodiment of the present specification, the unit represented by Formula 10 may be derived from a compound represented by Formula 11 below.

[Formula 11]

In Formula 11,

X3 and X4 are hydrogen; heavy hydrogen; It is a halogen group, and T1 and t1 are as defined in Formula 10.

In one embodiment of the present specification, the polymer may further include a repeating unit represented by Formula 12 or Formula 13 below.

[Formula 12]

[Formula 13]

a1, a2, b1, and b2 are the repeating numbers of the units in the parentheses, and are each independently an integer from 1 to 1,000, and the definitions of other substituents are the same as those in Formula 1.

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

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

According to an exemplary embodiment of the present specification, it may be a block polymer including a hydrophilic block containing a unit derived from the compound represented by Formula 1 and a hydrophobic block represented by Formula 10.

According to an exemplary embodiment of the present specification, preparing a monomer containing a compound represented by Formula 1; and homopolymerizing the monomer. The homopolymerization may be carried out under a Ni catalyst or a Pd catalyst. Additionally, nucleophilic reactions using dihydroxy monomers and dithiol monomers can also be used.

According to an exemplary embodiment of the present specification, preparing a monomer containing a compound represented by Chemical Formula 1; Preparing a second monomer containing a unit represented by Formula 10; and polymerizing the first and second monomers. The polymerization may proceed under a Ni catalyst or a Pd catalyst. Additionally, nucleophilic reactions using dihydroxy monomers and dithiol monomers can also be used.

In addition, the polymer manufactured by the manufacturing method according to an exemplary embodiment of the present specification transfers ions through a hydrophilic block and secures mechanical properties through a hydrophobic block, while containing sulfuric acid (- High ionic conductivity can be provided through the introduction of perfluorosulfonic acid (ex, -CF ₂ CF ₂ SO ₃ H), a super acid _, instead of SO 3 H). A polymer separator containing the above units has excellent ionic conductivity. Additionally, the unit is thermally and chemically stable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Ion conductivity (∂) = l/(R x d)

Here, l is the distance between the two electrodes (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 as S/cm.

In this specification, ionic conductivity may mean cationic conductivity.

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

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

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

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

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

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

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

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

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

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

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst layer can be formed by coating the catalyst ink directly on the separator or on the gas diffusion layer. At this time, the coating method of the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating, or spin coating methods may be used. Catalytic ink may typically consist of a catalyst, polymer ionomer, and solvent.

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

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

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

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

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

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

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

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

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

The fuel supply unit 80 serves to supply fuel to the stack 60, and includes a fuel tank 81 that stores fuel and a pump 82 that supplies the fuel stored in the fuel tank 81 to the stack 60. It can be configured. As fuel, gaseous or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol, or natural gas.

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

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

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

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

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

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

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

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

Example 1 - Perfluoro sulfonic acid containing monomer I

Perfluorosulfonic acid containing 3,5- in a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, nitrogen inlet, and mechanical stirrer. Add 5.000 g of difluoromonomer (Compound 1), 4.516 g of 4-chlorothiophenol, and 5.754 g of potassium carbonate (K ₂ CO ₃ ) and dissolve in 19 mL of anhydrous N-Methyl-2-pyrrolidone (NMP) for 12 hours at 100°C. reacted. The reaction was completed by pouring the reactant into distilled water, and extracted with ethyl acetate (EA). The extracted organic layer was additionally washed three times with distilled water containing potassium chloride (KCl), and the organic solvent was removed under reduced pressure to obtain Compound 2. The resulting product was recrystallized in water and dried under vacuum to prepare perfluorosulfonic acid-containing monomer I.

Figure 4 is a diagram showing the ¹ H-NMR spectrum of monomer I.

Figure 6 shows the LC-Mass results of monomer I.

Example 2 - Perfluoro sulfonic acid containing monomer II

Perfluorosulfonic acid containing 3,5- in a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, nitrogen inlet, and mechanical stirrer. Add 20.000 g of difluoromonomer (Compound 1), 18.066 g of 4-chlorothiophenol, and 23.019 g of potassium carbonate (K ₂ CO ₃ ), dissolve in 76 mL of anhydrous N-Methyl-2-pyrrolidone (NMP), and leave at 100°C for 12 hours. reacted. The reaction was completed by pouring the reactant into distilled water, and extracted with ethyl acetate (EA). The extracted organic layer was additionally washed three times with distilled water containing potassium chloride (KCl), and the organic solvent was removed under reduced pressure to obtain Compound 2. Afterwards, without any separate purification process, it was placed in a 500 mL round bottom flask, and 80 mL of hydrogen peroxide (aq. H ₂ O ₂ , 30%) and 240 mL of acetic acid were refluxed at 90°C for 20 hours. The reactant was cooled to room temperature and cooled at low temperature to obtain a white solid (Compound 3). The resulting composite was recrystallized from ethanol and dried under vacuum to prepare perfluorosulfonic acid-containing monomer II.

Figure 5 is a diagram showing the ¹ H-NMR spectrum of monomer II.

Figure 7 shows the LC-Mass results of monomer II.

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

Claims (11)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
L1 to L3 are the same or different from each other and are each independently directly bonded; -S-; -O-; ―SO ₂ ―; or -CO-,
A is ―SO ₃ H, ―SO ₃ ^- M ⁺ , ―COOH, ―COO ^- M ⁺ , ―PO ₃ H ₂ , ―PO ₃ H ^- M ⁺ , ―PO ₃ ^2- 2M ⁺ , ―O(CF ₂ ) _m SO ₃ H, ―O(CF ₂ ) _m SO ₃ ^- M ⁺ , ―O(CF ₂ ) _m COOH, ―O(CF ₂ ) _m COO ^- M ⁺ , ―O(CF _{2 )} ) _m PO ₃ H ₂ , ―O(CF ₂ ) _m PO ₃ H ^- M ⁺ , or ―O(CF ₂ ) _m PO ₃ ^2- 2M ⁺ ,
m is an integer from 2 to 6, M is a group 1 element,
R is hydrogen; halogen group; or a hydroxy group,
R1 to R10 are the same as or different from each other, and are each independently hydrogen; halogen group; or a hydroxy group,
At least one of R1 to R5 is a halogen group,
At least one of R6 to R10 is a halogen group,
k is an integer from 0 to 3, and when k is an integer of 2 or more, R is the same or different,
R11 and R12 are the same or different from each other and are each independently a halogen group,
n is an integer from 2 to 10, and when n is an integer of 2 or more, the structures within the parentheses are the same or different. In claim 1,
The L1 to L3 are the same as or different from each other, and each independently -S-; Or -SO ₂ - The compound. In claim 1,
A compound wherein L1 to L3 are the same. In claim 1,
The A is -O(CF ₂ ) _m SO ₃ H, or -O(CF ₂ ) _m SO ₃ ^{-M +} , m is an integer of 2 to 6, and M is a group 1 element. In claim 1,
The compound of Formula 1 is represented by the following Formula 2:
[Formula 2]

In Formula 2,
X1 and In claim 1,
A compound wherein R11 and R12 are F. A polymer comprising units derived from a compound according to any one of claims 1 to 6. A polymer separator comprising the polymer according to claim 7. anode; cathode; and a polymer separator according to claim 8 provided between the anode and the cathode. A membrane electrode assembly according to at least two claims 9;
A stack including a bipolar plate provided between the membrane electrode assemblies;
A fuel supply unit that supplies fuel to the stack; and
A polymer electrolyte fuel cell including an oxidizing agent supply unit that supplies an oxidizing agent to the stack. An anode cell containing an anode and an anode electrolyte;
A cathode cell containing a cathode and a cathode electrolyte; and
A redox flow battery comprising the polymer separator according to claim 8, which is provided between the anode cell and the cathode cell.