KR20200052757A - Electrochemical Stack - Google Patents

Abstract

A membrane electrode assembly (500) of the present invention includes: a polymer electrolyte membrane (502); a first electrochemical reaction layer (504) formed on one side of the polymer electrolyte membrane to conduct an oxidation reaction; a first electron conductive layer (506) formed between the polymer electrolyte membrane and the first electrochemical reaction layer; a second electrochemical reaction layer (508) formed on the other side of the polymer electrolyte membrane to conduct a reduction reaction; and a second electron conductive layer (518) formed between the polymer electrolyte membrane and the second electrochemical reaction layer.

Description

Electrochemical Stack {Electrochemical Stack}

The present invention relates to a stack having a membrane electrode assembly, more specifically, to make the device very compact, to reduce the manufacturing cost by reducing the number of parts, and to reduce the amount of electricity consumed during electrolysis by reducing the contact point and the membrane electrode assembly. It relates to the electrochemical cell used and the stack for electrochemistry.

In general, an electrochemical cell is an energy conversion device that uses electrical energy or generates electrical energy, and is classified into an electrolysis cell and a fuel cell. For practical use of the electrochemical cell, it is necessary to improve the power density in the case of a fuel cell (in the case of water electrolysis, decrease the consumption of electric energy), to improve durability and to lower the cost.

1 to 4 show a typical electrochemical cell unit structure, a stack structure for electrochemistry and a system structure.

1 is a conceptual diagram of a membrane electrode assembly 100 constituting a part of a typical electrolysis cell that electrochemically decomposes water to produce hydrogen gas and oxygen gas, and the lower portion of FIG. 1 shows the thickness of each component layer. .

The electrochemical cell for electrolysis that produces oxygen gas (O ₂ ) and hydrogen gas (H ₂ ) by electrolysis of water (H ₂ 0) includes a first electrochemical reaction layer 104 and a second electrochemical reaction layer ( 108), a film 106, a first diffusion layer 102 and a second diffusion layer 110. At this time, the first electrochemical reaction layer 104 is composed of a first electrochemical catalyst 112 and a first carrier 114, the second electrochemical reaction layer 108 is a second electrochemical catalyst 116 and It is composed of a second carrier (118).

The first diffusion layer 102 and the second diffusion layer 110 assist the transfer of electrons and reactants or products to (or in) the first and second electrochemical catalysts 112 and 116. The first and second electrochemical catalysts 112 and 116 are the most important materials for electrolysis or electric energy generation, and the first and second carriers 114 and 118 are first and second electrochemical catalysts 112 and 112, respectively. 116) provides the role of support and the electron's movement path.

The first and second electrochemical catalysts 112 and 116 are mixed together with the first and second carriers 114 and 118, a binder, and a solvent to form a slurry or paste. After being made, it is made of first and second electrochemical reaction layers 104 and 108 by applying to the film 106 or by applying to the first and second diffusion layers 102 and 110. At this time, the "electrochemical reaction layer (104, 108)-membrane 106" or "electrochemical reaction layer (104, 108)-membrane 106-diffusion layer (102, 110)" made in this way is a membrane electrode assembly ( It is called Membrane Electrode Assembly (hereinafter referred to as "MEA").

The gap between the first electrochemical reaction layer 104 and the second electrochemical reaction layer 108 formed in the MEA has a physical film thickness value, and the first electrochemical reaction layer 104 and the second electrochemical reaction layer ( 108) Since there are no air bubbles inside, operation of low voltage and high current is possible. In addition, since the conductivity of the electrolytic solution is not used as in the alkaline electrolysis cell, water as a raw material can be used with high purity, and thus there is an advantage of obtaining high purity hydrogen and oxygen.

The process of electrolysis of water using the configuration shown in FIG. 1 is as follows. Here, the place where the oxidation reaction takes place as the first electrochemical reaction layer 104, and the place where the reduction reaction occurs as the second electrochemical reaction layer 108, the oxidation reaction and the reduction reaction occur simultaneously.

First, when water (H ₂ 0) is supplied to the first electrochemical reaction layer 104 through the first diffusion layer 102, water generates a first electrochemical catalyst 112 (oxidation catalyst, positive electrode active material, oxygen gas) the decomposition reaction takes place by) and hydrogen ions (H ⁺⁾ (proton) ^- electrode), oxygen gas (O ₂₎ and e (e as shown below in Scheme 1. At this time, the oxygen gas (O ₂ ) is discharged to the outside of the electrolysis cell, and hydrogen ions (H ⁺ ) pass through the membrane 106 by the electric field to the second electrochemical catalyst 116 (reduction catalyst, cathode active material, See the hydrogen gas electrode), and electron (e ^-) is the first electrochemical catalyst 112 in the first diffusion layer 102, a second electrochemical through an external circuit (not shown) and a second diffusion layer (110) Move to catalyst 116.

On the other hand, the second electrochemical catalyst 116 in a hydrogen ion (H ⁺⁾ and electrons (e ^-) moved in a first electrochemical catalyst 112 is hydrogen gas (H ₂₎ as shown in Scheme 2 by the reaction are generated . Then, some of the water supplied to the first electrochemical reaction layer 104 moves to the second electrochemical reaction layer 108 by an electric field and flows out to the outside of the electrolysis cell together with hydrogen gas (H ₂ ).

Representing the electrochemical reactions occurring in the first electrochemical catalyst 112 and the second electrochemical catalyst 116, respectively, are as shown in Reaction Schemes 1 and 2 below.

[Scheme 1]

^{_{2H 2 O → 4H + + 4e}} - + O 2 ( positive electrode)

[Scheme 2]

_{^{4H + + 4e - → 2H 2}} ( cathode)

On the other hand, in the case of a fuel cell, reaction occurs inversely with the electrolysis of water, which will be described below.

First, hydrogen gas is introduced into the first electrochemical reaction layer, and oxygen gas is supplied to the second electrochemical reaction layer. Then, the hydrogen gas is converted into hydrogen ions (protons) and electrons by the electrochemical reaction in the first electrochemical catalyst, and the electrons pass through the membrane to the second electrochemical catalyst through an electrically connected external load. Then, in the second electrochemical catalyst, protons and electrons generated and moved in the first electrochemical catalyst react with oxygen gas supplied from the outside to generate water, energy, and heat.

2 is a structural diagram of a typical electrochemical cell for electrolysis of water with the MEA of FIG. 1. As shown in Figure 2, the electrochemical cell 200 is a first end plate 202 (End Plate), a first insulating plate 204, a first current supply plate 206, the first electrochemical reaction chamber frame 208, first electrochemical reaction chamber 210, MEA (100 in FIG. 1), second electrochemical reaction chamber 212, second electrochemical reaction chamber frame 214, second current supply plate 216 ), A second insulating plate 218 and a second end plate 220, and a DC power supply as a power conversion device 224 that supplies current to the electrochemical cell.

The first end plate 202 and the second end plate 220 provide bolt / nut fastening holes (not shown), passages of reactants and products (not shown) for assembling unit electrochemical cells, and a first insulating plate 204 and the second insulating plate 218 are electrically between the first end plate 202 and the first current supply plate 206 and between the second end plate 220 and the second current supply plate 216, respectively. The insulating function, the first current supply plate 206 and the second current supply plate 216 is connected to the power conversion device 224 serves to supply the current required for the electrochemical cell 200.

On the other hand, when the first electrochemical catalyst 112 is located in the first electrochemical reaction chamber 210 and an oxidation reaction occurs, it becomes a space for the movement of water as a reactant and oxygen as a product, and focuses on the membrane 106 In the second electrochemical reaction chamber 212 located on the opposite side of the first electrochemical reaction chamber 210, a space for the movement of hydrogen generated by the reduction reaction and water moved in the first electrochemical reaction chamber 210 Is provided.

The first electrochemical reaction chamber 210 is blocked from the outside by the first electrochemical reaction chamber frame 208, and the second electrochemical reaction chamber 212 is external by the second electrochemical reaction chamber frame 214. And is blocked. In addition, a gasket (or packing) 222 to prevent external leakage of reactants and products is installed between the MEA 100, the first electrochemical reaction chamber frame 208, and the second electrochemical reaction chamber frame 214. .

Among the components constituting the electrochemical cell 200, the first electrochemical reaction chamber frame 208, the second electrochemical reaction chamber frame 214, and the gasket 222 are introduced into the reactant or product through the electrochemical cell and It has a suitable hole to facilitate the outflow, and the first electrochemical reaction chamber frame 208 and the second electrochemical reaction chamber frame 214 are formed with a flow path (indicated by a dotted line in Fig. 2A).

Meanwhile, another electrochemical cell 200 is a pressure pad (not shown) for maintaining the balance of the electrochemical cell 200 between the second electrochemical reaction chamber frame 214 and the second current supply plate 216. 3, 304).

3 is a conceptual diagram of a conventional general electrochemical stack. In order to obtain a desired amount of product in an electrolysis reaction, a plurality of unit electrochemical cells are required. At this time, a conjugate of two or more electrochemical cells stacked is called an electrochemical stack.

As shown in FIG. 3, when the electrochemical cells are stacked to form the electrochemical stack 300, a desired number of unit electrochemical cells are repeatedly installed between the basic electrochemical cells 200. At this time, the pressure pad 304 that induces compression between components is installed between unit electrochemical cells. In the electrochemical stack, the unit electrochemical cells are assembled by a combination of a bolt 306 and a nut 310 through holes formed at the edges of the first and second end plates 202 and 220.

4 is a view showing a system for producing hydrogen by electrolysis of water using the electrolysis stack of the same concept as the electrochemical stack of FIG. The hydrogen generator system 400 illustrated in FIG. 4 purifies hydrogen gas generated from the electrolysis stack 420, a water treatment unit that processes water supplied to the electrolysis stack 420, and the electrolysis stack 420. It is composed of a gas processing unit that controls pressure.

As the raw material used for the electrolysis stack 420, 1Mega ohm cm or more of pure water is used, and pure water is supplied by the control of the automatic valve 402 installed in the pure water supply line s1, and the automatic valve 402 is regulated. It is controlled by the level sensor 405 for detecting the water level in the oxygen-water separation tank 404 (dotted line e2). Water in the oxygen-water separation tank 404 is supplied to the electrolysis stack 420 by a circulation pump 406 installed in the circulation pipe (s2), and the circulation line (s9) circulated in the hydrogen-water separator (424) Combined with the heat exchanger 408, the water quality sensor 410 and the ion exchange filter 412 through the piping is installed, to the first electrochemical reaction chamber 414 of the electrolysis stack 420 (where oxidation reaction occurs) Is supplied. On the other hand, when a direct current is supplied to the electrolysis stack 420 through the electric wire e1 in the power converter 440, a water decomposition reaction occurs.

Oxygen and unreacted water generated in the first electrochemical reaction chamber 414 are moved to the oxygen-water separation tank 404 through the discharge pipe s4, and the temperature sensor 416 monitors the temperature in the discharge pipe s4. ) Is installed. The oxygen separated from the oxygen-water separation tank 404 is discharged to the outside through the oxygen discharge pipe s5, and the water undergoes a recirculation process.

Hydrogen gas generated in the second electrochemical reaction chamber 422 is accompanied by water, and is moved to a hydrogen-water separation tank 424 through a discharge pipe s6 to separate gas and water. The hydrogen-water separation tank 424 is provided with a level sensor 426 for water level detection for water level adjustment. If the water level of the hydrogen-water separation tank 424 is higher than a certain value, the automatic valve 428 is opened (electrical signal e3) and is supplied to the circulation pipe s2 through the circulation line s9.

Meanwhile, the hydrogen gas separated from the hydrogen-water separation tank 424 is supplied to the hydrogen gas purifier 430 through a gas pipe s7 to remove moisture contained in the hydrogen. In general, the hydrogen gas purifier 430 is applied with a bed filled with a hygroscopic agent. The hydrogen that has passed through the hydrogen gas purifier 430 is supplied to a site requiring hydrogen through a high purity hydrogen gas pipe (s8). At this time, the high-purity hydrogen gas pipe (s8) has a pressure control valve 434 for regulating the pressure of hydrogen, the pressure of the hydrogen gas generated in the electrolysis stack 420 is adjusted. Pressure sensors 432 and 438 for measuring pressure are installed at the front end and the rear end of the pressure regulating valve 434, and check valves 436 are installed to maintain the flow of gas in a predetermined direction.

The conventional MEA 100, the electrochemical cell 200, the electrochemical stack 300, and the hydrogen generator system 400 have the following characteristics.

First, as can be seen in FIGS. 1 to 3, the electron movement path is the first electrochemical catalyst 112 → the first diffusion layer 102 → the first electrochemical reaction chamber frame 208 → the first current supply plate ( 206) → Power converter 224 → Second current supply plate 216 → Pressure pad 304 → Second electrochemical reaction chamber frame 214 → Second diffusion layer 110 → Second electrochemical catalyst 116 ).

Second, as can be seen in Figure 1, the path of movement of the proton consists of a first electrochemical catalyst 112 → membrane 106 → second electrochemical catalyst 116.

Third, the unit electrochemical cell includes a first electrochemical reaction chamber 210 in which an electrochemical reaction occurs by the first electrochemical catalyst 112 and a second electrochemical reaction in which the second electrochemical catalyst 116 occurs. Each of the electrochemical reaction chambers 212 has a space. That is, the unit electrochemical cell has two electrochemical reaction chamber spaces.

Fourth, the first electrochemical reaction chamber 210 is formed by the structure of the first electrochemical reaction chamber frame 208, and the second electrochemical reaction chamber 212 is of the second electrochemical reaction chamber frame 214. It is formed by the structure. Accordingly, the spaces of the first and second electrochemical reaction chambers 210 and 212 are the paths of electrons traveling through the solids of the first and second electrochemical reaction chamber frames 208 and 214, and the first and second A path for the movement of electrons and electrolytes (see FIG. 2 (a)) is provided while the paths of reactants and products, which are gases or liquids moving through the empty spaces of the electrochemical reaction chamber frames 208 and 214 collide.

In water electrolysis, the tasks for practical use of an electrochemical cell are reduction of electric energy consumption (in the case of a fuel cell, improvement of output density), improvement of durability, and cost reduction. In this regard, the conventional MEA 100, an electrochemical cell 200 and the electrochemical stack 300 has the following problems.

First, as shown in FIGS. 1 and 2, the movement path of electrons generated in the first electrochemical catalyst 112 is greater than or equal to about 215 μm in one path and greater than or equal to 430 μm (215x2) in both paths. Similarly, when the electrochemical stack 300 is configured, an electron movement path and a contact point increase exponentially, resulting in energy loss due to a voltage drop at the contact point, thereby reducing electrolysis efficiency. That is, there is a disadvantage in that the energy consumption during electrolysis becomes very large.

Second, as shown in FIG. 2, the structure of the electrochemical cell 200 has a structure in which electrons and reactants / products move in the directions of the first electrochemical catalyst and the second electrochemical catalyst (ie, in the same direction). Therefore, since the movement paths of the electrons moving along the solid and the reactants / products moving along the empty space must be secured, it causes a increase in manufacturing cost due to having a complicated flow path as shown in Fig. 2A.

Third, since the electrochemical cell 200 is composed of a first electrochemical reaction chamber frame 208 and a second electrochemical reaction chamber frame 214, that is, two electrolytic chambers, many electrochemical cell stacks 300 are formed. Components are required, which increases costs and degrades performance.

Fourth, when constructing a plurality of unit electrochemical cells in the stack 300 for electrochemistry, high processing precision of the components is required in order to make the contact between each component uniform and maintain the desired pressure. Cost increases.

Fifth, when configuring a plurality of unit electrochemical cells in the stack 300 for electrochemistry, in order to maintain uniform pressure between the components and to maintain the desired pressure, the end plate and the clamping coupling the same. ) The structure of the system is complicated, and a lot of torque is required for clamping using the bolt 306 and the nut 310, which causes a cost increase.

Republic of Korea Patent Registration No. 10-1357146 Republic of Korea Patent Publication No. 10-2008-0032962

Therefore, the present invention is to solve the above problems, by separating the electron movement path and the fluid movement path to reduce the electrical energy consumption, improve the durability, and reduce the manufacturing cost membrane electrode assembly and electricity using the same We want to provide a stack for chemical cells and electrochemistry.

In addition, the present invention makes the device very compact by embedding two MEA electrochemical reaction layers in the electrochemical reaction chamber where oxidation and reduction reactions occur, and significantly reduces the number of parts, significantly reducing the manufacturing cost of the electrochemical cell. In addition, it is intended to provide a membrane electrode assembly and an electrochemical cell and an electrochemical stack using the same, as well as a membrane electrode assembly that can significantly reduce the amount of electricity consumed during electrolysis by significantly reducing the contact point that causes an increase in electrical resistance. .

The membrane electrode assembly of the present invention for achieving the above object is a polymer electrolyte membrane, a first electrochemical reaction layer formed on one side of the polymer electrolyte membrane to undergo an oxidation reaction, the polymer electrolyte membrane and the first electrochemistry A first electroconductive layer formed between the reaction layers, a second electrochemical reaction layer formed on the other side of the polymer electrolyte membrane and a reduction reaction occurs, and formed between the polymer electrolyte membrane and the second electrochemical reaction layer It characterized in that it comprises a second electron conductive layer.

Further, according to the present invention, the first electron conductive layer and the second electron conductive layer are characterized in that each has a thickness of 0.1 ~ 5㎛.

Further, according to the present invention, the first electron conductive layer and the second electron conductive layer are any one of platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, and manganese. It is characterized by being configured.

In addition, according to the present invention, the first electrochemical reaction layer and the second electrochemical reaction layer are each made of catalyst ink, and the catalyst ink is characterized by comprising an electrochemical catalyst, a carrier, a polymer electrolyte and a solvent. .

In addition, according to the present invention, the electrochemical catalyst is any of platinum, palladium, ruthenium, iridium, rhodium, and osmium platinum group elements, iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium and aluminum. It is characterized by being composed of any one of one metal, their alloys, oxides and complex oxides.

In addition, according to this invention, the electrochemical catalyst is characterized by having a particle diameter of 0.5 ~ 20㎚.

In addition, according to the present invention, the carrier is characterized by consisting of any one of titanium oxide, carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotubes and fullerene.

In addition, according to this invention, the carrier is characterized by having a particle diameter of 10 ~ 1,000 ㎚.

The electrochemical cell of the present invention for achieving the above object, the membrane electrode assembly configured as described above, the oxidation or reduction reaction occurs, and the membrane electrode assembly in a form capable of supplying and discharging reactants and products accordingly The first and second electrochemical reaction chamber frames, the first and second insulating plates and the first and second end plates, which are sequentially arranged on both sides, are connected to the first and second electrochemical reaction chamber frames, respectively. The first and second electrochemical reaction chamber frames have an electrochemical reaction chamber that receives the first and second electrochemical reaction layers of the membrane electrode assembly, respectively. It is characterized by.

The stack for electrochemistry of the present invention for achieving the above object is a plurality of membrane electrode assembly configured as described above, an oxidation reaction or a reduction reaction occurs and the supply and discharge of reactants and products accordingly occurs inside The first and second electrochemical reaction chamber frames, which are sequentially arranged on both sides in the outward direction, are disposed between the first and second insulating plates and the first and second end plates, and the plurality of membrane electrode assemblies to perform the same oxidation. A plurality of third electrochemical reaction chamber frames each having an electrochemical reaction chamber accommodating two of the first electrochemical reaction layer or the second electrochemical reaction layer of the membrane electrode assembly having a reaction or reduction reaction property, and the agent It is characterized in that it comprises a power conversion device that is connected to each of the first, second, and third electrochemical reaction chamber frames to supply current.

In the present invention, the anode catalyst → electron conducting layer on the membrane → external circuit → electron conducting layer on the membrane → electron transfer path is formed in the order of cathode catalyst, so the anode catalyst → anode chamber diffusion layer → anode chamber current supply plate → external circuit → Pressure pad → Cathode chamber current supply plate → Cathode chamber diffusion layer → Cathode catalyst In order to have a shorter electron movement path than the conventional electrochemical cell in which the electron movement path is formed, the current density-voltage characteristic of the electrochemical cell becomes excellent, and The energy consumption during decomposition can be reduced.

In addition, since the present invention embeds two electrochemical reaction layers of MEA in the electrochemical reaction chamber, the device becomes very compact, and when constructing the electrochemical stack, the number of parts can be significantly reduced compared to the conventional electrochemical cell. The manufacturing cost of the electrochemical cell can be significantly reduced.

In addition, in the present invention, since the number of component parts is significantly reduced compared to a conventional electrochemical cell when constructing an electrochemical stack, the contact point that causes an increase in electrical resistance can be significantly reduced compared to a conventional electrochemical cell, thereby reducing the amount of electricity consumed during electrolysis. Not only can it be drastically reduced, but it can also reduce operating costs.

1 is a conceptual diagram of MEA, which is a part of a typical electrolysis cell for electrochemically decomposing water to produce hydrogen gas and oxygen gas.
2 is a structural diagram of a typical electrochemical cell for electrolysis of water with the MEA of FIG. 1.
3 is a conceptual diagram of a conventional general electrochemical stack.
4 is a view showing a system for producing hydrogen by electrolysis of water using the electrochemical stack of FIG.
5 is a view showing a MEA according to an embodiment of the present invention.
FIG. 6 is a structural diagram of an electrochemical cell having MEA shown in FIG. 5.
7 is a conceptual diagram of an electrochemical stack constructed by stacking electrochemical cells in FIG. 6.
8 is a graph comparing the performance of Inventive Example 1 and Comparative Example 1 according to the present invention.
9 is a graph comparing the performance of Inventive Example 2 and Comparative Example 2 according to the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment that can be easily carried out by those of ordinary skill in the art to which this invention pertains. However, in the detailed description of the operation principle of the preferred embodiment of the present invention, if it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, the same reference numerals are used for parts having similar functions and functions throughout the drawings.

5 is a view showing a MEA according to an embodiment of the present invention. As shown in FIG. 5, the MEA 500 according to an embodiment of the present invention includes a first electron conducting layer 506, a first electrochemical reaction layer 504, a film 502, and a second electron conducting layer 518, the second electrochemical reaction layer 508. At this time, the first electron conductive layer 506 and the first electrochemical reaction layer 504 are sequentially formed on one side of the film 502, and the second electron conductive layer 518 and the second electrochemical reaction layer 508 ) Are sequentially formed on the other side of the film 502.

The electrolysis reaction of water occurring in the MEA 500 of this embodiment is as follows. Here, the first electrochemical catalyst will be described as an oxidation reaction (oxygen generation reaction) occurs, and the second electrochemical catalyst will be a reduction reaction (hydrogen generation reaction).

First, when water (H ₂ 0) is supplied to the first electrochemical catalyst 510 (oxidation catalyst, oxygen catalyst), oxygen gas (O ₂ ), electrons (e ⁻ ) and hydrogen ions (H ⁺ ) (proton) Decomposes into At this time, a part of the water (H ₂ 0) flows out with oxygen gas (O ₂ ), and the decomposed hydrogen ion (H ⁺ ) passes through the membrane 502 to the second electrochemical catalyst 516 (reduction) Pole, hydrogen pole). Then, electrons are moved along the first electron conductive layer 506 formed on the film 502 and an external circuit (not shown). Meanwhile, electrons (e ⁻ ) moved along an external circuit (not shown) connecting the first electron conductive layer 506 and the second electron conductive layer 518 and decomposed and moved by the first electrochemical catalyst 510 Hydrogen ions are reacted to produce hydrogen gas. In addition, water (H ₂ 0) passing through the membrane 502 along with hydrogen ions (H ⁺ ) flows out of the electrolysis cell together with hydrogen gas. At this time, the electrochemical reactions occurring in the first electrochemical catalyst 510 and the second electrochemical catalyst 516 are the same as those of Reaction Schemes 1 and 2 mentioned above.

The membrane 502 of this embodiment may be any one having hydrogen ion (proton) conductivity, and a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte may be used. At this time, as the fluorine-based polymer membrane, for example, Nafion (Nafion, registered trademark) of DuPont, Flemion (Flemion, registered trademark) of Asahi Glass Co., Ltd., Aciplex (Asiplex, registered trademark of Asahi Kasei Co., Ltd.) ), Gore's Gore Select (Gore Select, registered trademark), etc. may be used, and hydrocarbon-based polymer membranes include sulfonated polyether ketones, sulfonated polyethersulfones, sulfonated polyetherethersulfones, sulfonated polysulfides, An electrolyte membrane such as sulfonated polyphenylene can be used. Among these, it is suitable to use Nafion (registered trademark) -based material of DuPont as a polymer film.

The first and second electron conductive layers 506 and 518 of this embodiment are formed on both sides of the film 502 and function as electron conduction. At this time, the thickness of the first and second electron conductive layers 506 and 518 formed on the film 502 is 0.1 to 5 μm, and preferably 0.5 to 3 μm. For this reason, when the thickness of the first and second electron conductive layers 506 and 518 is 0.1 μm or less, an increase in resistance occurs when electrons move through the electron conductive layer, and when the thickness of the electron conductive layer is 5 μm or more, excessive electrons This is because the formation of a conductive layer interferes with the movement of protons, resulting in a problem of low ion conductivity. The materials of the first and second electron conductive layers 506 and 518 include platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, and manganese, which have excellent conductivity. Metals are possible and platinum group is preferred from the viewpoint of chemical resistance.

The first and second electrochemical reaction layers 504 and 508 of this embodiment are formed on both sides of the film 502 having the first and second electron conductive layers 506 and 518, and are formed using catalyst ink. do. The catalyst ink for the first electrochemical reaction layer 504 includes at least a first electrochemical catalyst 510, a carrier 512, a polymer electrolyte and a solvent, and a catalyst ink for the second electrochemical reaction layer 508 Includes at least a second electrochemical catalyst 516, a carrier 514, a polymer electrolyte, and a solvent.

As the polymer electrolyte included in the catalyst ink of this embodiment, a fluorine-based polymer electrolyte having a proton conductivity, a hydrocarbon-based polymer electrolyte, or the like can be used. And, as the fluorine-based polymer electrolyte, for example, Nafion (registered trademark) -based material of DuPont may be used, and as the hydrocarbon-based polymer electrolyte, sulfonated polyether ketone, sulfonated polyether sulfone, and sulfonated polyether ether Electrolytes such as sulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used. In particular, considering the adhesion between the first and second electrochemical reaction layers 504 and 508 and the first and second electron conductive layers 506 and 518, it is preferable to use the same material as the film 502.

The first and second electrochemical catalysts 510 and 516 used in this embodiment include platinum, palladium, ruthenium, iridium, rhodium, and osmium platinum group elements, iron, lead, copper, chromium, cobalt, nickel, manganese, and vanadium. , Molybdenum, gallium, aluminum, metals or alloys thereof, or oxides, complex oxides, etc. may be used, and the electrode reactivity is excellent, and the electrode reaction is efficiently and stably used for a long period of time. Platinum, palladium, It is preferred that one or two or more metals or oxides selected from rhodium, ruthenium and iridium are used.

In the first and second electrochemical catalysts 510 and 516 of this embodiment, if the particle size is too large, the activity of the catalyst decreases, and if the particle size is too small, the stability of the catalyst decreases, so the particle size is preferably 0.5 to 20 nm. , More preferably 1 to 5 nm.

Meanwhile, the carrier (or carrier) 512, 514 supporting the catalyst is an electronically conductive powder, and titanium oxide and carbon particles are used. These carriers have a fine particle shape and conductivity, and any material may be used as long as they do not invade the catalyst, but titanium oxide, carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotubes, and fullerene are used. It is desirable to be.

In addition, when the particle diameter is too small, the carriers 512 and 514 have difficulty in forming an electron conductive path, and if the particle diameter is too large, gas diffusivity to the electrode catalyst layer formed on the carrier decreases or the utilization rate of the catalyst decreases. Therefore, the particle size is preferably 10 to 1,000 nm, more preferably 10 to 100 nm.

The size Dc of the film 502 of this embodiment is greater than or equal to the size of the first and second electrochemical reaction chamber frames 606 and 612 described in FIG. 6, and the first and second electron conductive layers 506 and 518 ), The size (Db) is less than the size of the first and second electrochemical reaction chamber frames 606 and 612 described in FIG. 6, and the sizes of the first and second electrochemical reaction layers 504 and 508 (Da) ) Is preferably made to coincide with the inner areas of the first and second electrochemical reaction chambers 608 and 610.

Hereinafter, a method of manufacturing MEA according to an embodiment of the present invention will be described.

1st process: pretreatment process of the film 502

The pre-treatment of the film 502 is a process of roughening the surface of the film by a mechanical method and physically and chemically treating organic and inorganic impurities present in the film 502. A detailed process of this will be described later.

Second process: Formation process of first and second electron conductive layers 506 and 518

After the film 502 obtained in the first process is immersed in a metal precursor solution for a certain period of time, a metal thin film layer having an electron conductivity function is formed on the film 502 through a reduction process. At this time, the thickness of the metal thin film layer is repeatedly formed by a deposition reduction process. A detailed process of this will be described later.

3rd process: the process of forming the first and second electrochemical reaction layers 504 and 508

A process for forming the first and second electrochemical reaction layers 504 and 508 on the film 502 having the first and second electron conductive layers 506 and 518 obtained in the second process. It consists of a manufacturing process, a catalyst ink transfer process, and a thermocompression process. The catalyst synthesis process is a process of obtaining a mixed oxide through the reaction of a desired catalyst precursor with an oxidizing agent, and drying it to obtain a powder structured electrochemical catalyst, and the catalyst ink manufacturing process is performed with the electrochemical catalyst synthesized in the catalyst synthesis process. It is a process to manufacture catalyst ink in which powder, dispersant, and binder of membrane 502 are mixed. In addition, the catalyst ink transfer process is a process in which the catalyst ink prepared in the catalyst ink manufacturing process is transferred onto a Teflon sheet using a spray or the like, and then dried, and the thermal compression process is performed on the first and second electron conductive layers obtained in the second process. This is a process of fixing the Teflon sheet obtained in the catalytic ink transfer process on both surfaces of the film 502 having (506, 518) and then thermocompressing it using a hot press or the like. A detailed process of this will be described later.

FIG. 6 is a structural diagram of an electrochemical cell having MEA shown in FIG. 5. 6, the electrochemical cell 600 of this embodiment includes a first end plate 602, a first insulating plate 604, a first electrochemical reaction chamber frame 606, and a first electrochemical reaction chamber. 608, MEA 500, a second electrochemical reaction chamber 610, a second electrochemical reaction chamber frame 612, a second insulating plate 614, and a second end plate 616, which is composed of electricity In order to drive the chemical cell 600, a DC power supply is used as the power converter 618.

A bolt / nut fastening hole (not shown) for assembling the electrochemical cell 600 is formed in the first end plate 602 and the second end plate 616, and a passage (not shown) through which reactants and products move ) Is provided. The first insulating plate 604 and the second insulating plate 614 function as an electrolytic component and an electrical insulation between the first end plate 602 and the second end plate 616, and the first electrochemical reaction chamber frame ( 606) and the second electrochemical reaction chamber frame 612 is connected to the power conversion device 618 and serves to supply the current required for the electrochemical cell 600.

In the electrochemical cell 600 of this embodiment, the first electrochemical reaction chamber 608 in which an oxidation reaction (oxygen reaction) occurs and the second electrochemical reaction chamber 610 in which a reduction reaction (hydrogen reaction) occurs are MEA 500 It has a form facing each other with the center. Meanwhile, the first electrochemical reaction chamber frame 606 serves to block the first electrochemical reaction chamber 608 from the outside, and the second electrochemical reaction chamber frame 612 is the second electrochemical reaction chamber 610 ) And serves to block the outside, and the first and second electrochemical reaction chamber frames 606 and 612 face each other around the MEA 500.

The first and second electrochemical reaction chamber frames 606 and 612 have suitable holes to facilitate inflow and outflow of reactants or products generated by the electrochemical reaction required for the electrochemical cell 600, and draw and withdraw current. A terminal for authorization may be provided.

7 is a conceptual diagram of an electrochemical stack constructed by stacking electrochemical cells in FIG. 6. As shown in FIG. 7, the electrochemical stack 700 of this embodiment is constructed by repeatedly installing a desired number (eg, n) of unit electrochemical cells between the basic electrochemical cells 600. . At this time, a plurality of MEA 500 is installed between the unit electrochemical cells, the third having a first electrochemical reaction chamber 702 or a second electrochemical reaction chamber 704 on both sides of the MEA 500, respectively. The electrochemical reaction chamber frames are repeatedly installed to be alternately arranged.

The first electrochemical reaction chamber 702 has a structure that accommodates the first electrochemical reaction layer 710a of the first MEA 708a and the second electrochemical reaction layer 710b of the second MEA 708b, The second electrochemical reaction chamber 704 has a structure that accommodates the second electrochemical reaction layer 712b of the second MEA 708b and the third electrochemical reaction layer 712c of the third MEA 708c. That is, two electrochemical reaction layers each having the same oxidation or reduction reaction properties are accommodated in each electrochemical reaction chamber.

The first and second electrochemical reaction chamber frames 606 and 612 serve to block the first and second electrochemical reaction chambers 702 and 704, respectively, from the outside. On the other hand, the first, second, and third electrochemical reaction chamber frames 606 and 612 are connected to a power conversion device 618, when inducing an oxidation reaction to provide an environment for each electrochemical reaction ( The +) pole is connected to the power converter 618, and when inducing a reduction reaction, the (-) pole is connected to the power converter 618.

The electrochemical cells in the electrochemical stack 700 of this embodiment are assembled by a combination of bolts 720 and nuts through holes formed in the first and second end plates 602 and 616.

In the following, the method of manufacturing the membrane electrode assembly for the inventive examples and the comparative examples of this embodiment will be described in detail, and the experimental results of each other will be described. However, this invention is not limited to the following invention examples.

[Inventive Example 1]

1. MEA (500) Manufacturing

(1) 1st process: pretreatment process of the film 502

The membranes 502 and Nafion 117 are scratched on both sides in 4 directions using sandpaper (Emery Sand Paper 1100CW) and then subjected to a swelling process in 90 ° C pure water. After the swelling process, impurities are removed through ultrasonic treatment in pure water, and then treated in 3% hydrogen peroxide (H ₂ O ₂ ) and 90 ° C. 0.5 to 1M sulfuric acid (H ₂ SO ₄ ) for 30 minutes, and then the pure water process is performed again. Repeat.

(2) Second process: Formation process of first and second electron conductive layers 506 and 518

The film 502 subjected to the first process is immersed in a precursor solution of platinum chloride ((NH ₃ ) ₄ PtCl ₂ * H ₂ O) for 5 hours. The polymer electrolyte membrane that has undergone the deposition process is washed with pure water, and the NaBH ₄ solution is divided and dropped every 20 minutes for a total of 2 hours to reduce the metal precursor. The polymer electrolyte membrane having the reduced electron layer is immersed in a NaOH solution at 90 ° C. for 1 hour, washed again with pure water, and the above impregnation reduction process is repeated as many times as desired, and the first and second electrons are deposited on the membrane 502. Conductive layers 506 and 518 are formed.

(3) Third process: first and second electrochemical reaction layer (504, 508) forming process

The process of forming the first and second electrochemical reaction layers 504 and 508 includes the first and second electrochemical reaction layers 504, on the film 502 having the first and second electron conductive layers 506 and 518. As a process for forming 508, the first and second electrochemical catalysts 510 and 516 synthesis process, the first and second electrochemical catalysts 510 and 516 ink manufacturing process, the first and second electrochemical catalysts ( 510, 516) and an ink transfer process.

(3-1) 3-1 process: synthesis process of first and second electrochemical catalysts 510 and 516

(3-1-1) Synthesis of the first electrochemical catalyst 510

An iridium ruthenium mixed catalyst oxidized through a reaction of iridium chloride (IrCl _{3 ·} xH ₂ O) and ruthenium chloride (RuCl _{3 ·} xH ₂ O) in a sodium nitrate solution was prepared. Then, iridium chloride and ruthenium chloride were stirred for 2 hours in a solution in which sodium nitrate was dissolved, and uniformly dissolved. The mixed catalyst solution prepared above was heated to 100 ° C and concentrated by evaporating distilled water for 1 hour, and then sintered at 475 ° C for 1 hour in an electric furnace and then cooled slowly. Then, it was filtered by washing with 9 L of distilled water to remove the resulting sodium chloride. The resulting solid was dried at 80 ° C. for 12 hours to prepare a final iridium ruthenium electrochemical mixed catalyst.

(3-1-2) Synthesis of second electrochemical catalyst 516

As the second electrochemical catalyst 516, commercialized Pt / C (Premetek, platinum wall mass 30%) was used.

(3-2) 3-2 process: ink manufacturing process of the first and second electrochemical catalysts 510 and 516

(3-2-1) Preparation of ink for the first electrochemical catalyst (510, oxygen-side catalyst)

Iridium ruthenium oxide catalyst prepared in the 3-1 process, nano-sized titanium dioxide as a carrier, and Nafion solution as a binder were used, and the used catalyst and the Nafion ionomer were isopropyl alcohol so that the solid weight was 1: 3.5. Mixed in solvent. In order to disperse the catalyst, stirring and ultrasonic waves were alternately treated twice for 1 hour.

(3-2-2) Preparation of ink for second electrochemical catalyst (516, hydrogen-side catalyst)

As the second electrochemical catalyst 516, Pt / C (Premetek, platinum mass 30%), and a Nafion solution (registered product, DuPont) were used as a binder. The catalyst used and the Nafion solution were mixed in an isopropyl alcohol solvent so that the solid weight was 1: 7.5. In order to disperse the catalyst, stirring and ultrasonic waves were alternately treated twice for 1 hour.

(3-3) 3-3 process: transfer process of first and second electrochemical catalysts 510 and 516

(3-3-1) First electrochemical reaction layer 504 transfer

Polytetrafluoroethylene (PTFE) sheet was used as the transfer sheet. The electrochemical catalyst layer is prepared by transferring the ink of the first electrochemical catalyst 510 obtained in the step 3-2 to an electrospray syringe, transferring the catalyst ink onto the substrate and drying it at 90 ° C. for 30 minutes in an atmospheric atmosphere. Did. The thickness of the first electrochemical reaction layer 504 was adjusted so that the supported amount of the oxide catalyst was about 4 mg / cm 2.

(3-3-1) Second electrochemical reaction layer 518 transfer

The electrochemical catalyst layer was prepared by transferring the ink of the second electrochemical catalyst 516 obtained in the step 3-2 to an electrospray syringe, transferring it to a carbon sheet, and drying it at 90 ° C. for 30 minutes in an atmospheric atmosphere. The thickness of the second electrochemical reaction layer 518 was adjusted so that the supported amount of the oxide catalyst was about 1 mg / cm 2.

(3-4) 3-4 process: thermocompression process

(3-4-1) Formation of first electrochemical reaction layer 504

The first electrochemical catalyst 510 loaded on the membrane 502 obtained in the second process over the Teflon sheet obtained in the process 3-3 was thermally compressed twice for 3 minutes at a pressure of 10 MPa at 120 ° C. The catalyst was transferred by removing the Teflon sheet.

(3-4-2) Formation of second electrochemical reaction layer 508

The carbon sheet loaded with the second electrochemical catalyst 516 prepared above on the opposite surface of the membrane 502 to which the first electrochemical reaction layer 504 prepared above is combined is subjected to a pressure of 10 MPa at 120 ° C. By heat-pressing for 2 minutes, MEA 500 as shown in FIG. 5 was obtained.

2. Evaluation electrochemical cell and evaluation system

The MEA of Inventive Example 1 has an electrochemically active area of 314 cm ² (Da = 20 cm), an electron conductive layer thickness of 0.5 mm, Db = 21 cm, an area of 346 cm ² , and a membrane size Dc = 25 cm. The evaluation was performed by laminating titanium fiber fibers on the first electrochemical reaction layer 504 and carbon fiber fibers having high diffusivity on the second electrochemical reaction layer 508. The evaluation was performed by actually fabricating a cell for evaluation of the concept shown in FIG. 2 and a water electrolysis system of the concept shown in FIG. 4.

The cell temperature was maintained at 80 ° C (416 temperature sensor in FIG. 4), and current-voltage measurement of the electrolysis cell was performed. Meanwhile, the discharge pressure of hydrogen (adjusted using s8 and 434 in FIG. 4) was maintained at about 10 bar.

3. Measurement result

8, it can be seen that the MEA produced by Inventive Example 1 had a small change in voltage even when the current density increased.

[Comparative Example 1]

1. MEA manufacturing (MEA manufacturing according to conventional methods)

The pretreatment process of the film and the formation of the first and second electrochemical reaction layers were performed in the same manner and conditions as those of Inventive Example 1, and the forming processes of the first and second electron conductive layers were compared with Inventive Example 1. Did not proceed.

2. Evaluation electrochemical cell and evaluation system

The same evaluation was performed on the MEA of Comparative Example 1 (electrochemically active area 314 cm 2) in the electrochemical cell of Example 1 and the evaluation system.

3. Measurement result

As shown in FIG. 8, it can be seen that the voltage increases significantly as the current density increases.

[Evaluation of Inventive Example 1 and Comparative Example 1]

FIG. 8 shows the current density-voltage characteristics of MEA for Inventive Example 1 and Comparative Example 1, where (1) is an area where superior performance of the electrochemical catalyst is exhibited, and (2) is a high current density area. . Since the composition of the electrochemical catalyst of Inventive Example 1 and the electrochemical catalyst of Comparative Example 1 are the same, as shown in FIG. 8, it can be seen that the membrane of Inventive Example 1 and the membrane of Comparative Example 1 exhibit similar performance in the region (1). have. By the way, it can be seen that the film having the electron conductive layer of Inventive Example 1 exhibits excellent electron conductivity to the electrochemical reaction layer, and thus exhibits low voltage characteristics in the region (2), which is a high-density current region, compared to the film of Comparative Example 1.

[Inventive Example 2]

1. MEA Manufacturing

MEA was prepared according to the same method and conditions as Inventive Example 1.

2. Electrochemical stack and evaluation system

MEA of Inventive Example 1 was fabricated and evaluated as the electrochemical stack shown in FIG. 7. At this time, the area of the electrochemical catalyst layer was 314 cm 2, and the size of the electrochemical stack was 10 unit electrochemical cells stacked. The operating conditions were conducted at the same temperature and pressure as Example 1 of the invention.

3. Measurement result

As shown in FIG. 9, it can be seen that the MEA produced by Inventive Example 2 had a small change in power consumption even when the current density increased.

[Comparative Example 2]

1. MEA Manufacturing

MEA was prepared according to the same method and conditions as Comparative Example 1.

2. Electrochemical Stack

The MEA of Comparative Example 1 was fabricated and evaluated as the electrochemical stack shown in FIG. 3. As in Inventive Example 2, the area of the electrochemical catalyst layer was 314 cm 2, and the scale of the electrochemical stack was stacked with 10 unit electrochemical cells. The operating conditions were conducted at the same temperature and pressure as Example 1 of the invention.

All. Measurement result

9, it can be seen that as the current density increases, the power consumption amount increases significantly.

[Evaluation of Inventive Example 2 and Comparative Example 2]

FIG. 9 shows the current density-power consumption characteristics of the electrochemical stacks for Inventive Example 2 and Comparative Example 2, where (1) is an area in which performance superiority is exhibited by an electrochemical catalyst, and (2) is an area. This is the area indicated by the superiority of performance by the rest of the components besides the electrochemical catalyst. As shown in FIG. 9, in the area (1), the electrochemical catalysts of Inventive Example 2 and Comparative Example 2 have the same structure, and it can be seen that the electrochemical stack exhibits similar performance. However, since the structure of the electrochemical stack having the electron conductive layer of Inventive Example 2 is excellent in electron conductivity, it can be seen that when producing hydrogen, it consumes low energy compared to the electrochemical stack of Comparative Example 2 in the region (2). .

As described above, the present invention is superior to the conventional electrochemical cell, that is, because it has a short electron migration path, the current density-voltage characteristic of the electrochemical cell is excellent, thereby reducing energy consumption during electrolysis. In other words, in the prior art, an electron transfer path was formed in the order of anode catalyst → anode chamber diffusion layer → anode chamber current supply plate → external circuit → pressure pad → cathode chamber current supply plate → cathode chamber diffusion layer → cathode catalyst. → The electron transfer path is formed in this order: electron conducting layer on the membrane → external circuit → electron conducting layer on the membrane → cathode catalyst. Therefore, the present invention has a shorter electron movement path than a conventional electrochemical cell, and because of this short electron movement path, the current density-voltage characteristic of the electrochemical cell is excellent, so that energy consumption during electrolysis can be reduced.

In addition, since the present invention accommodates each of two electrochemical reaction layers of MEA in the electrochemical reaction chamber, the apparatus becomes very compact, and when constructing the electrochemical stack, the number of parts is significantly greater than that of a conventional electrochemical cell. Since it can be reduced, the manufacturing cost of the electrochemical cell can be significantly reduced. In other words, when constructing n electrochemical cells, the electrochemical stack of the present invention has the number of parts as shown in Table 1, since the electrochemical reaction layers each receive two electrochemical reaction layers of the MEA, whereas The electrochemical stack of is formed to have a much larger number of parts than the electrochemical stack of the present invention.

Conventional electrochemical stack Stack for electrochemistry of the invention N = 1 N = 2 N = 3 N = 4 N = n N = 1 N = 2 N = 3 N = 4 N = n End plate 2 2 2 2 2 2 2 2 2 Diffusion layer 2 4 6 8 2n Pressure pad One 2 3 4 n Electrochemical reaction room
frame 2 4 6 8 2n 3 4 5 n + 1 MEA One 2 3 4 n 2 3 4 n sum 8 14 20 26 6n + 2 7 9 11 2n + 3

In addition, since the number of component parts of the present invention is significantly reduced compared to that of a conventional electrochemical cell when constructing an electrochemical stack as described above, the contact point that causes an increase in electrical resistance is significantly reduced than that of a conventional electrochemical cell as shown in Table 2. This can greatly reduce the amount of electricity consumed during electrolysis, as well as reduce operating costs.

Existing electrochemical stack Stack for electrochemistry of the invention N = 1 N = 2 N = 3 N = 4 N = n N = 1 N = 2 N = 3 N = 4 N = n Contact resistance 6 11 16 21 5n + 5 4 8 12 16 4n

As described above, in the detailed description of the present invention, preferred embodiments of the present invention have been described, but these are illustrative examples of the best embodiments of the present invention, but are not intended to limit the present invention. In addition, it is of course possible for anyone who has ordinary knowledge in the technical field to which the present invention pertains to various modifications and imitation without departing from the scope of the technical idea of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the equivalents as well as the claims described below.

500: membrane electrode assembly 504, 508: electrochemical reaction layer
502: membrane 510, 516: electrochemical catalyst
512, 514: carrier 600: electrochemical cell
602, 616: end plate 604, 614: insulating plate
606, 612: electrochemical reaction chamber frame
608, 610: electrochemical reaction chamber 700: electrochemical stack

Claims (10)

A polymer electrolyte membrane,
A first electrochemical reaction layer formed on one side of the polymer electrolyte membrane and undergoing an oxidation reaction,
A first electron conducting layer formed between the polymer electrolyte membrane and the first electrochemical reaction layer,
A second electrochemical reaction layer formed on the other side of the polymer electrolyte membrane and undergoing a reduction reaction, and
And a second electron conductive layer formed between the polymer electrolyte membrane and the second electrochemical reaction layer. The method according to claim 1,
The first electron-conducting layer and the second electron-conducting layer, each having a thickness of 0.1 ~ 5㎛ membrane electrode assembly. The method according to claim 1,
The first electron-conducting layer and the second electron-conducting layer are made of any one of platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, and manganese. Electrode assembly. The method according to claim 1,
Each of the first electrochemical reaction layer and the second electrochemical reaction layer is made of a catalyst ink, and the catalyst ink comprises an electrochemical catalyst, a carrier, a polymer electrolyte, and a solvent. The method according to claim 4,
The electrochemical catalyst is a platinum group element of platinum, palladium, ruthenium, iridium, rhodium, osmium, metal of any one of iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium and aluminum, and alloys thereof , Membrane electrode assembly, characterized in that it is composed of any one of oxide and double oxide. The method according to claim 4,
The electrochemical catalyst is a membrane electrode assembly characterized in that it has a particle diameter of 0.5 ~ 20㎚. The method according to claim 4,
The carrier is a titanium electrode, carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotubes and full-length membrane electrode assembly, characterized in that made of any one of fullerene. The method according to claim 4,
The carrier is a membrane electrode assembly, characterized in that having a particle diameter of 10 ~ 1,000㎚. The membrane electrode assembly according to any one of claims 1 to 8 (Membrane Electrode Assembly),
First and second electrochemical reaction chamber frames, first and second, which are sequentially arranged on both sides based on the membrane electrode assembly in a form in which an oxidation reaction or a reduction reaction occurs and supply and discharge of reactants and products accordingly Insulation plate and first and second end plates,
And a power conversion device connected to the first and second electrochemical reaction chamber frames to supply current.
The first and second electrochemical reaction chamber frames are electrochemical cells, each having an electrochemical reaction chamber that receives the first and second electrochemical reaction layers of the membrane electrode assembly, respectively. A plurality of membrane electrode assembly (Membrane Electrode Assembly) according to any one of claims 1 to 8,
First and second electrochemical reaction chamber frames, first and second insulating plates, which are sequentially arranged on both sides from the inside to the outside in a form in which an oxidation reaction or a reduction reaction occurs and supply and discharge of reactants and products accordingly, and The first and second end plates,
Electrochemical reaction chambers disposed between the plurality of membrane electrode assemblies to receive two of the first electrochemical reaction layer or the second electrochemical reaction layer of the membrane electrode assembly having the same oxidation reaction or reduction reaction properties, respectively A plurality of third electrochemical reaction chamber frames, and
And a power conversion device connected to the first, second, and third electrochemical reaction chamber frames to supply current.

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