EP4556597A1 - Elektrolysevorrichtung und betriebsverfahren dafür - Google Patents

Elektrolysevorrichtung und betriebsverfahren dafür Download PDF

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Publication number
EP4556597A1
EP4556597A1 EP23875176.2A EP23875176A EP4556597A1 EP 4556597 A1 EP4556597 A1 EP 4556597A1 EP 23875176 A EP23875176 A EP 23875176A EP 4556597 A1 EP4556597 A1 EP 4556597A1
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Prior art keywords
electrolysis
cathode
kpa
anode
electrolysis device
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English (en)
French (fr)
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EP4556597A4 (de
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Tai Min NOH
Tae Geun Noh
Kwang Hwan Kim
Jong Jin Lee
Dae Hwan Kim
In Kyoung AHN
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LG Chem Ltd
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell

Definitions

  • the present invention relates to an electrolysis device for electrolyzing carbon dioxide and a method for operating the device.
  • Carbon dioxide is a greenhouse gas that causes global warming, and thus, should be reduced.
  • methods such as capture, chemical conversion, or electrochemical conversion are known.
  • the electrochemical conversion method allows for a precise control of components so as to produce other synthetic gases, which is more economically beneficial than simply removing carbon dioxide.
  • carbon dioxide may be electrolyzed together with water to obtain carbon monoxide, ethylene, methane, formic acid, formate, various hydrocarbons, and an organic substance such as an aldehyde or an alcohol.
  • a process of electrochemically decomposing carbon dioxide is similar to a technique of electrolyzing water. However, since the activity of an electrochemical reaction improves in a strong base atmosphere, an aqueous KOH solution of a certain concentration is generally used as an electrolyte solution.
  • an aqueous KOH solution of a certain concentration is generally used as an electrolyte solution.
  • the transferred electron reacts with carbon dioxide and water supplied to the cathode and then is decomposed into carbon monoxide and a hydroxide ion (OH - ), and the generated hydroxide ion reacts with a hydrogen ion (H + ) of an anode to produce water, thereby being in an electrical neutral state.
  • an electrochemical decomposition reaction of carbon dioxide is completed.
  • the water supplied together with the carbon dioxide reacts with the transferred electron, which is separate from the carbon monoxide production reaction, and is electrolyzed, thereby producing hydrogen gas, and at the same time, producing a hydroxide ion.
  • Such a reaction of water and an electron may be said to have a competitive relationship with the carbon monoxide production reaction. Since the reactions are electrochemical reactions, the generation amount of carbon monoxide and a ratio of hydrogen/carbon dioxide may be easily controlled by controlling a voltage.
  • Patent Document 001 JP 2022-042280 A
  • An aspect of the present invention provides an electrolysis device, wherein a back pressure is applied to the inside of a cathode outlet of the electrolysis device to prevent a phenomenon in which an electrolyte solution flows from an anode to a cathode and to maintain electrolysis efficiency at an excellent level.
  • Another aspect of the present invention provides a method for operating an electrolysis device, wherein a back pressure is applied to the inside of a cathode outlet of the electrolysis device to reduce the flow rate of a product and unreacted carbon dioxide to be discharged, thereby improving the rate of use of supplied carbon dioxide.
  • the present invention provides an electrolysis device and a method for operating the same.
  • an electrolysis device of the present invention a back pressure is applied to a cathode outlet to prevent a phenomenon in which an electrolyte solution flows from an anode to a cathode when an electrochemical reaction is performed, and as a result, electrolysis efficiency and overvoltage may be maintained at an excellent level.
  • the amount of carbon dioxide used in an electrochemical reaction may be increased even if the same carbon dioxide is supplied, so that the conversion rate of carbon dioxide and the Faraday efficiency of carbon monoxide may be increased, and the consumption of power for recirculating unreacted carbon dioxide may be reduced.
  • a method for operating an electrolysis device of the present invention includes supplying an electrolyte solution through an anode inlet to an electrolysis stack in which one or more electrolysis cells including an anode, a cathode, a separator, and an electrolyte solution are stacked, and supplying a reactant through a cathode inlet S1, performing an electrolysis reaction on the reactant in the electrolysis stack S2, and discharging a product produced by the electrolysis reaction of the step S2 and an unreacted reactant through a cathode outlet to the outside of the electrolysis stack S3, wherein in the step S3, a back pressure of about 10 kPa to about 50 kPa is applied to the product and the unreacted reactant discharged through the cathode outlet.
  • the electrolysis device of the present invention may include an electrolysis cell or an electrolysis stack in which two or more electrolysis cells are stacked, a cathode inlet, a cathode outlet, an anode inlet, and an anode outlet.
  • the electrolysis cell may include an anode, a cathode, a separator disposed between the anode and the cathode, and an electrolyte solution.
  • the electrolysis cell may form a membrane electrode assembly having a zero-gap structure in which a gas diffusion layer, a cathode, a separator, and an anode with an electrolyte flow path are sequentially stacked, and in this case, separator plates may be disposed on both sides of the membrane electrode assembly to form one cell.
  • the cathode inlet may serve to supply reactants to the electrolysis cell, and may be disposed adjacent to the cathode.
  • the cathode outlet may serve to discharge products produced by an electrochemical reaction and unreacted reactants from the electrolysis cell to the outside, and may be disposed adjacent to the cathode.
  • the anode inlet may serve to supply the electrolyte solution into the electrolysis cell or stack, and the anode outlet may serve to discharge the used electrolyte solution to the outside after the electrolysis reaction.
  • a method for supplying carbon dioxide, which is a reactant, to an electrolysis cell by increasing the flow rate and flow speed of the carbon dioxide is used, while operating an electrolysis device under the atmospheric pressure condition.
  • the conversion rate may be increased by increasing the amount of introduced carbon dioxide, but the amount of carbon dioxide unreacted inside the electrolysis cell and discharged again increases, and the unreacted carbon dioxide is required to be circulated again and introduced into the electrolysis cell, so that the consumption of current and power used for circulating the carbon dioxide is significant.
  • the greater the amount of the unreacted carbon dioxide the greater the cost and time consumed in a process of classifying the unreacted carbon dioxide and a product discharged theretogether.
  • the method for operating an electrolysis device of the present invention maintains the flow rate and flow speed of supplied carbon dioxide constant during the electrolysis reaction, but reduces the flow rate of a product and unreacted carbon dioxide discharged from the cathode outlet, thereby allowing sufficiently more carbon dioxide to react inside the electrolysis cell. That is, the method for operating an electrolysis device of the present invention may pressurize the inside of the cathode outlet to increase the pressure inside the electrolysis cell and/or stack, thereby increasing the amount of reacted carbon dioxide, and accordingly, the rate of use of carbon dioxide and the Faraday efficiency of carbon monoxide may be improved.
  • the method for operating an electrolysis device of the present invention may be performed through supplying carbon dioxide to the electrolysis device S1, electrolyzing the carbon dioxide S2, and discharging a product produced by electrolyzing the carbon dioxide and unreacted carbon dioxide S3, wherein the discharging of the product and the unreacted carbon dioxide of the step S3 may be performed by applying a back pressure to the product and the unreacted reactant to be discharged.
  • the back pressure refers to a resistive pressure acting in a direction opposite to a direction in which a fluid flows when the fluid is discharged through a tube.
  • a cathode outlet of the present invention may include a pressure control valve to be described below, wherein the back pressure may be controlled by changing a width of the cathode outlet through the opening and closing of the pressure control valve, and a pressure may be applied in a direction opposite to a direction in which a product and an unreacted reactant to be discharged through the cathode outlet are discharged.
  • a back pressure of about 10 kPa to about 50 kPa may be applied to the product and the unreacted reactant discharged through the cathode outlet.
  • the back pressure may be about 10 kPa or greater, about 13 kPa or greater, about 15 kPa or greater, about 17 kPa or greater, about 20 kPa or greater, about 22 kPa or greater, about 25 kPa or greater, about 27 kPa or greater, about 32 kPa or greater, about 50 kPa or less, about 47 kPa or less, about 45 kPa or less, about 42 kPa or less, about 40 kPa or less, about 37 kPa or less, about 35 kPa or less, about 32 kPa or less, or about 30 kPa or less.
  • a pressure applied to a product and an unreacted reactant to be discharged is low, resulting in a small amount of reduction in the flow rate of the product and the unreacted reactant to be discharged, so that it is difficult to expect an improvement in the rate of use of carbon dioxide and the Faraday efficiency of carbon monoxide.
  • a pressure applied to a product and an unreacted reactant to be discharged is high, resulting in a reduced amount of a product reacted inside the electrolysis cell, and the conversion rate of carbon dioxide may be decreased, and the overvoltage may be increased.
  • an internal pressure of the cathode outlet and an internal pressure of the anode inlet may be controlled to satisfy Equation 1 below.
  • the loss of an electrolyte solution is reduced to about 0.1 L/day or less, and an electrolysis device may be continuously operated without degradation in electrolysis efficiency.
  • the internal pressure of a cathode outlet is less than the internal pressure of an anode inlet, an electrolyte solution penetrates a separator and is transferred to the cathode outlet, and the loss of an electrolyte solution corresponds to a level of about 0.5 L/h, making it difficult to drive an electrolysis device continuously.
  • the electrolyte solution may have a loss flow rate of about 0.1 L/day or less.
  • the loss flow rate of the electrolyte solution may be about 0.1 L/day or less, about 0.09 L/day or less, about 0.08 L/day or less, about 0.07 L/day or less, about 0.06 L/day or less, about 0.05 L/day or less, about 0.04 L/day or less, about 0.03 L/day or less, about 0.02 L/day or less, or about 0.01 L/day or less.
  • the loss flow rate corresponds to a level of about 0.5 L/h or greater, and in this case, an amount of a salt generated by an electrolysis solution flowing to a cathode through a separator increases, so that a continuous electrical conversion reaction is impossible.
  • the loss flow rate of the electrolyte solution is measured by an amount of the electrolyte solution lost over time with respect to an initial amount of the electrolyte solution contained inside the electrolysis cell.
  • the supply flow rate of the reactant may be maintained constant during an electrolysis reaction.
  • the method for operating an electrolysis device of the present invention maintains the supply flow rate and flow speed of carbon dioxide supplied to an electrolysis cell constant, but controls the discharge flow rate of a product and unreacted carbon dioxide discharged, so that the rate of use of carbon dioxide may be increased.
  • the method for operating an electrolysis device of the present invention may solve a limitation, the limitation which may occur when a supply flow rate and a flow rate are typically increased, in which the rate of use of carbon dioxide is decreased, and the amount of unreacted carbon dioxide recirculated into the electrolysis cell is increased.
  • the unreacted reactant discharged in the step S3 may be circulated back into the electrolysis cell.
  • the method for operating an electrolysis device of the present invention may reduce an amount of unreacted carbon dioxide by increasing the rate of use of carbon dioxide, and thus, may reduce the consumption of power which may be used for circulating the unreacted carbon dioxide back into the electrolysis cell.
  • the method for operating an electrolysis device of the present invention may increase the Faraday efficiency of carbon monoxide to reduce the consumption of a driving current applied to an electrolysis device.
  • the cathode outlet includes a pressure control valve, and a pressure on the product and the unreacted reactant may be controlled by opening and closing the pressure control valve.
  • the cathode outlet of the electrolysis device of the present invention may include a pressure control valve, and a pressure inside the cathode outlet may be controlled by opening or closing the pressure control valve. The pressure inside the cathode outlet may be increased by closing the pressure control valve, and the flow rate may be decreased by applying a pressure to the product and the unreacted carbon dioxide.
  • the electrolysis cell includes a cathode, an anode and a separator, wherein the separator may be a porous separator, and particularly, may be a porous separator having hydrophilic properties.
  • the porous separator may be an ion-selective exchange membrane, and the porous separator may include an anion exchange membrane, a cation exchange membrane, or an amphoteric ion exchange membrane.
  • the porous separator may include a hydrophilic porous substrate, and thus, may allow a moisture content to be maintained at a certain level.
  • the porous separator includes a porous substrate including pores having an average particle diameter of about 10 nm to about 750 nm, and thus, may provide a path for allowing various molecules including ions and water molecules to be smoothly transferred by an aqueous solution-based electrolyte, and accordingly, the carbon dioxide conversion rate may be increased, and the overvoltage may be reduced during the operation of the electrolysis device.
  • the hydrophilic porous substrate may be a cellulose-based resin.
  • the hydrophilic porous substrate may be a cellulose-based resin, and the cellulose-based resin may be one or more selected from the group consisting of cellulose acetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetylpropionate, cellulose diacetate, cellulose dibutyrate, cellulose tributyrate, and cellulose nitrate.
  • the porous substrate contained in the porous separator included in the electrolysis cell of the present invention may include cellulose acetate.
  • the cellulose acetate has hydrophilic properties, has high mechanical and chemical strength due to high dimensional limitation which does not allow dimensions and shapes to be changed under conditions such as temperature or humidity, and has a uniform pore structure.
  • a porous separator used in an electrolysis cell for converting carbon dioxide pores formed in the porous separator are impregnated with an aqueous solution-based electrolyte solution, and ions such as HCO 3 - , CO 3 2- , and OH - may be transferred through the pores.
  • cellulose acetate having the hydrophilic properties, high mechanical strength, and an uniform pore size is used as a separator of a carbon dioxide electrolysis cell using an aqueous solution-based electrolyte solution, properties of a high carbon dioxide conversion rate, high Faraday efficiency of carbon monoxide, and a low overvoltage may be exhibited.
  • the method for operating an electrolysis device of the present invention uses a large-area electrolysis unit cell of about 100 cm 2 or greater including the above-described porous separator, and thus, may be applied to a high-performance unit cell or a stack in which a plurality of unit cells are stacked.
  • the electrolysis device of the present invention includes an electrolysis stack in which one or more electrolysis cells including an anode, a cathode, a separator, and an electrolyte solution are stacked, an anode inlet connected to the anode to transfer the electrolyte solution, and a cathode outlet connected to the cathode to discharge a product and an unreacted reactant from the cathode, wherein in the cathode outlet, a back pressure is applied to the product and the unreacted reactant discharged from the cathode outlet.
  • the electrolysis device of the present invention may include an electrolysis cell or an electrolysis stack in which two or more electrolysis cells are stacked, a cathode inlet, a cathode outlet, an anode inlet, and an anode outlet.
  • the electrolysis cell may include an anode, a cathode, a separator disposed between the anode and the cathode, and an electrolyte solution, and in order to increase a driving voltage and current efficiency, the electrolysis cell may form a membrane electrode assembly having a zero-gap structure in which a gas diffusion layer, a cathode, a separator, and an anode with an electrolyte flow path are sequentially stacked, and in this case, separator plates may be disposed on both sides of the membrane electrode assembly to form one cell.
  • the electrolysis device of the present invention is the same as described in the method for operating an electrolysis device of the present specification.
  • the back pressure is about 10 kPa to about 50 kPa, and is the same as described in the method for operating an electrolysis device of the present specification. Additionally, if the above back pressure range is satisfied and an internal pressure of the cathode outlet is equal to or higher than an internal pressure of the anode inlet, the loss of the anode transferred from the anode to the cathode is reduced, and the electrolysis device may be continuously operated with high efficiency.
  • the internal pressure of the cathode outlet of the electrolysis device may be about 10 kPa to about 300 kPa, and the internal pressure of the anode outlet may be about 5 kPa to about 60 kPa.
  • the internal pressure of the cathode outlet of the electrolysis device may be about 10 kPa or greater, about 30 kPa or greater, about 50 kPa or greater, about 60 kPa or greater, about 70 kPa or greater, about 90 kPa or greater, about 100 kPa or greater, about 110 kPa or greater, about 120 kPa or greater, about 130 kPa or greater, about 300 kPa or less, about 270 kPa or less, about 230 kPa or less, about 220 kPa or less, about 210 kPa or less, about 200 kPa or less, about 190 kPa or less, about 170 kPa or less, about 160 kPa or less, about
  • the internal pressure of the anode outlet may be about 5 kPa or greater, about 7 kPa or greater, about 9 kPa or greater, about 10 kPa or greater, about 12 kPa or greater, about 15 kPa or greater, about 20 kPa or greater, about 22 kPa or greater, about 25 kPa or greater, about 27 kPa or greater, about 30 kPa or greater, about 60 kPa or less, about 57 kPa or less, about 55 kPa or less, about 53 kPa or less, about 50 kPa or less, about 48 kPa or less, about 45 kPa or less, about 42 kPa or less, about 40 kPa or less, about 39 kPa or less, about 37 kPa or less, or about 35 kPa or less.
  • the cathode outlet may include a pressure control valve, wherein the back pressure may be controlled through the pressure control valve, and the contents related to the pressure control valve and the back pressure control are the same as described in the method for operating an electrolysis device of the present specification.
  • an internal pressure of the cathode outlet and an internal pressure of the anode inlet may be controlled to satisfy Equation 1 below.
  • the loss of an electrolyte solution is reduced to about 0.1 L/day or less, and an electrolysis device may be continuously operated without degradation in electrolysis efficiency.
  • the internal pressure of a cathode outlet is less than the internal pressure of an anode inlet, an electrolyte solution penetrates a separator and is transferred to the cathode outlet, and the loss of an electrolyte solution corresponds to a level of about 0.5 L/h, making it difficult to drive an electrolysis device continuously.
  • the electrolyte solution may have a loss flow rate of about 0.1 L/day or less.
  • the loss flow rate of the electrolyte solution may be about 0.1 L/day or less, about 0.09 L/day or less, about 0.08 L/day or less, about 0.07 L/day or less, about 0.06 L/day or less, about 0.05 L/day or less, about 0.04 L/day or less, about 0.03 L/day or less, about 0.02 L/day or less, or about 0.01 L/day or less.
  • the loss flow rate corresponds to a level of about 0.5 L/h or greater, and in this case, an amount of a salt generated by an electrolysis solution flowing to a cathode through a separator increases, so that a continuous electrical conversion reaction is impossible.
  • the loss flow rate of the electrolyte solution is measured by an amount of the electrolyte solution lost over time with respect to an initial amount of the electrolyte solution contained inside the electrolysis cell.
  • FIG. 1 is a graph of voltage and current data of a long-term performance evaluation of Example 5
  • FIG. 2 is a graph of carbon dioxide and hydrogen Faraday efficiency data of the long-term performance evaluation of Example 5
  • FIG. 3 is a graph of voltage and current data of a long-term performance evaluation of Comparative Example 5.
  • the cell or stack may be formed in a large area in order to increase the conversion amount of carbon dioxide or water per unit time.
  • the electrolysis cell or stack it is important to maintain the large area for a long period of time and at the same time to maintain physical/chemical durability and high electrolysis efficiency.
  • the area of an applied separator also increases, and accordingly, the supply flow rate of a reaction gas also increases, and when a large amount of reaction gas is supplied into the cell or stack, the internal pressure thereof also increases, so that a pressure gradient is created between an anode and a cathode based on the separator, causing a phenomenon in which materials of both electrodes are mixed with each other through the separator.
  • the pressure relationship between the cathode outlet and the anode inlet is controlled at a certain ratio even under the condition of such a large-scale cell or stack, resulting in the development of an electrolysis device which maintains long-term durability without the mixing of materials of both electrodes and has high electrolysis efficiency.
  • the electrolysis stack may have an electrode area of about 500 cm 2 to about 5,000 cm 2 .
  • the electrode area of the electrolysis stack refers to an area in which an electrolysis reaction is activated, and the electrode area of such an electrolysis stack may be about 500 cm 2 to about 5,000 cm 2 .
  • the electrolysis stack may have an electrode area of about 500 cm 2 or larger, about 600 cm 2 or larger, about 700 cm 2 or larger, about 800 cm 2 or larger, about 1,000 cm 2 or larger, about 1,200 cm 2 or larger, about 1,500 cm 2 or larger, about 2,000 cm 2 or larger, about 2,500 cm 2 or larger, about 5,000 cm 2 or smaller, about 4,500 cm 2 or smaller, about 4,300 cm 2 or smaller, about 4,100 cm 2 or smaller, about 4,000 cm 2 or smaller, about 3,800 cm 2 or smaller, about 3,500 cm 2 or smaller, about 3,300 cm 2 or smaller, about 3,100 cm 2 or smaller, about 3,000 cm 2 or smaller, specifically, about 1,000 cm 2 to about 4,000 cm 2 .
  • the electrolysis device of the present invention includes a cell or stack satisfying the above-described electrode area range, and thus, may maintain high electrolysis efficiency per unit time and high physical/chemical durability for a long period of time.
  • the electrolysis device may be used in all of the field of electrochemical conversion, and the electrolysis device may be a fuel cell, a device capable of producing useful chemicals through electrochemical conversion such as water electrolysis, or a device which may be utilized for reducing and converting carbon dioxide and NOx.
  • the electrolysis device may be an electrochemical conversion device which converts carbon dioxide into carbon monoxide and ethylene.
  • the electrolysis device may include a cell or stack which converts introduced carbon dioxide into carbon monoxide, and the cell or stack may include an anode, a cathode, an electrolyte, and a separator.
  • the cell may be a membrane electrode assembly (MEA) having a zero-gap structure in which a gas diffusion layer, a cathode, a separator, and an anode with an electrolyte flow path are sequentially stacked.
  • MEA membrane electrode assembly
  • the electrolysis refers to decomposing a material through a redox reaction by applying a direct current voltage to perform a decomposition reaction which does not occur spontaneously.
  • the anode is an oxidation electrode which oxidizes water to generate oxygen, at which time, a hydrogen ion is generated.
  • the hydrogen ion generated in the anode is transferred to the cathode through the electrolyte, and the cathode is a reduction electrode in which a reactant introduced into the cathode may react with an electron the hydrogen ions transferred from the anode and generate a product.
  • the separator may be disposed between the anode and the cathode.
  • the separator itself may be composed of an inert material that does not participate in an electrochemical reaction, but provides a path for allowing an ion to be transferred between the anode and the cathode, and may serve to separate a physical contact of the anode and the cathode.
  • the anode and the cathode of the electrolysis device of the present invention may each include a catalyst layer.
  • the cathode in the cathode region, water vapor supplied with carbon dioxide generates a reduction product by an electroreduction reaction on the surface of the cathode.
  • the cathode may include a gas diffusion layer to evenly supply humidified carbon dioxide gas to the cathode region. If the cathode includes a hydrophobic gas diffusion layer, it is possible to smoothly diffuse, distribute, and supply supplied carbon dioxide to the catalyst layer of the cathode.
  • the hydrophobic gas diffusion layer effectively prevents moisture condensation, thereby allowing the supply of carbon dioxide to be continuously uniform, and at the same time, allowing an electrolysis reaction to smoothly progress.
  • the catalyst layer may have a surface having a porous structure or the like to well exert gas permeation properties on the surface.
  • the anode may include a catalyst active in the electrolysis of water, and the catalyst layer of the anode may include one or more selected from the group consisting of Pt, Au, Pd, Ir, Ag, Rh, Ru, Ni, Al, Mo, Cr, Cu, Ti, W, an alloy thereof, or a mixed metal oxide, e.g., Ta 2 0 5 , Ir0 2 , etc., for an oxygen generation reaction.
  • the anode may include titanium (Ti) coated with iridium oxide (IrO 2 ).
  • the catalyst layer of the cathode may include one or more selected from the group consisting of Sn, an Sn alloy, Al, Au, Ag, C, Cd, Co, Cr, Cu, an Cu alloy, Ga, Hg, In, Mo, Nb, Ni, NiCo 2 O 4 , an Ni alloy, an Ni-Fe alloy, Pb, Rh, Ti, V, W, Zn, and a mixture thereof.
  • the cathode may contain silver (Ag).
  • a cation exchange membrane or an anion exchange membrane (AEM) may be included.
  • the cation exchange membrane may serve as a membrane which prevents a reduction material generated in the cathode by catalysis from being transferred to the anode and oxidized, and may be a separation phase which suppresses transmission of an anion and allows the transmission of a cation such as a hydrogen ion (H + ).
  • a hydrogen ion (H + ) is generated in the anode by oxidizing water, and an excessive amount of the hydrogen ion flows to the cathode to saturate an active portion of the catalyst in which carbon dioxide is converted, which may cause a problem in which the conversion rate of carbon dioxide is decreased.
  • the anion exchange membrane may reduce the amount of the hydrogen ion flowing to the cathode.
  • the anion exchange membrane blocks the transfer of the hydrogen ion, and thus, may prevent carbon dioxide conversion performance of the cathode from degrading, and may refer to a separation phase which allows the transmission of an anion such as OH - , HCO 3 - , and CO 3 2- .
  • one or more electrolyte selected from the group consisting of KHCO 3 , K 2 CO 3 , KOH, KCl, KClO 4 , K 2 SiO 3 , Na 2 SO 4 , NaNO 3 , NaCl, NaF, NaClO 4 CaCl 2 , Cs 2 CO 3 , H 3 PO 4 , KHPO 4 , guanidinium cation, H + cation, alkali metal cation, ammonium cation, alkyl ammonium cation, halide ion, alkyl amine, borate, carbonate, guanidinium derivative, nitrite, nitrate, phosphate, polyphosphate, perchlorate, silicate, sulfate, tetraalkyl ammonium salt, or an aqueous solution containing a mixture thereof may be used, and specifically, the electrolyte of the carbon dioxide electrolysis device of the present invention may include an aqueous solution containing a mixture
  • the gas diffusion layer may use a porous body using a carbon material such as carbon fiber cloth, carbon fiber felt, carbon fiber paper, or the like, or a metal porous body made of a thin metal plate having a net structure such as expanded metal, metal mesh, or the like, and in the carbon dioxide electrolysis device of the present invention, the gas diffusion layer may use carbon fiber cloth.
  • the electrolysis device may be utilized in all fields that require electrochemical conversion, and particularly, allows a desired product to be obtained by electrochemically decomposing carbon dioxide, and specifically, the electrolysis device may electrolyze carbon dioxide to produce one or more selected from the group consisting of carbon monoxide, ethylene, methane, formic acid, hydrocarbon, aldehyde, and alcohol.
  • a carbon dioxide electrolysis device having operating conditions described below was operated.
  • Example 2 The same procedure as in Example 1 was performed, except that a reaction current density of about 200 mA/cm 2 was applied.
  • Example 2 The same procedure as in Example 1 was performed, except that the reaction current density was about 200 mA/cm 2 , the electrode area was about 1,000 cm 2 , the 40 °C Humidified CO 2 gas supply flow was about 6,000 ml/min, and the flow rate of the anode electrolyte was about 2 L/min.
  • the reaction current density was about 200 mA/cm 2
  • the electrode area was about 1000 cm 2
  • the 40 °C Humidified CO 2 gas supply flow was about 18000 ml/min
  • the flow rate of the anode electrolyte was about 3 L/min.
  • the electrode area was about 1000 cm 2
  • the 40 °C Humidified CO 2 gas supply flow was about 18000 ml/min
  • the flow rate of the anode electrolyte was about 3 L/min.
  • Example 1 The same procedure as in Example 1 was performed, except that no pressure was applied to the cathode outlet.
  • Example 2 The same procedure as in Example 1 was performed, except that no pressure was applied to the cathode outlet and a reaction current density of about 200 mA/cm 2 was applied.
  • Example 2 The same procedure as in Example 1 was performed, except that the reaction current density was about 200 mA/cm 2 , the electrode area was about 1,000 cm 2 , the 40 °C Humidified CO2 gas supply flow was about 6,000 ml/min, the flow rate of the anode electrolyte was about 2 L/min, and no pressure was applied to the cathode outlet.
  • Example 5 The same procedure as in Example 5 was performed, except that no pressure was applied to the cathode outlet.
  • a carbon dioxide electrolysis device was operated using the operation methods according to Examples 1 to 6 and Comparative Examples 1 to 4. Electrolysis was performed using the carbon dioxide electrolysis device, at which time the conversion rate (%) of carbon monoxide, the CO Faraday efficiency (%) of carbon monoxide, and the voltage were measured, and the measurement result values are shown in Table 1. In addition, a long-term performance evaluation was performed on Example 5 and Comparative Example 5, and the evaluation results are shown in FIGS. 1 to 3 .
  • the conversion rate (%) was calculated as the ratio of produced carbon monoxide (CO) with respect to the amount of introduced carbon dioxide (CO 2 ) gas per hour.
  • Equation 1 Q is a flow rate at a cathode outlet, F is a Faraday constant, p is a pressure, T is a measurement temperature, and R is an ideal gas constant.
  • a total current i total is a value of the total current applied over time, and a current i product with respect to a product is a value calculated from a volume of gas V product measured through GC analysis.
  • the application of a current and the measurement of a voltage were performed through a VSP potentiostat of BioLogic Co.
  • An 80 A booster was mounted to apply a current corresponding to a large area.
  • the application of the current was performed in stages of 200 mA/cm 2 and 300 mA/cm 2 , respectively, and was maintained for a predetermined period of time, after which the voltage was recorded at the time when the time of 20 minutes had elapsed. At this time, the Gas-Chromatography (GC) analysis was simultaneously performed.
  • GC Gas-Chromatography
  • the carbon dioxide electrolysis devices of Example 5 and Comparative Example 5 were operated for at least 200 hours, and the conversion rate of carbon monoxide, the Faraday efficiency of carbon monoxide, the Faraday efficiency of hydrogen, the reaction current density and the overvoltage of Example 5, and the reaction current density and the overvoltage of Comparative Example 5 were measured in the same manner as in the above-described measurement methods.
  • Example 1 Classificat ion Cathode inlet flow rate (ml/min ) Current density (mA/ cm 2 ) Applied pressur e (bar) Faraday efficie ncy (%) Carbon dioxide convers ion rate Overvol tage (V)
  • Example 1 800 300 0.4 89.0 25.35 -3.53
  • Example 2 800 300 0.2 91.3 26.01 -3.507
  • Example 3 800 200 0.4 93.6 17.78 -3.209
  • Example 5 18000 200 0.3 92 19.8 -9.41
  • Example 6 18000 300 0.5 88 29.2 -10.1 Comparative Example 1 800 300 0 89.0 25.35 -3.778 Comparative Example 2 800 300 0.6 87.4 24.88 -3.561 Comparative Example 3 800 200 0 90.3 17.70 -3.286 Comparative Example 4 6000 200 0 89.7 20.52 -4.235
  • Examples 1 to 4 a suitable pressure was applied to the cathode outlet, in Comparative Examples 1, 3, and 4, no pressure was applied to the cathode outlet, and in Comparative Example 2, a pressure out of the suitable pressure range according to the method for operating an electrolysis device of the present invention was applied to the cathode outlet.
  • Examples 1 to 2 in all of which the same current density was applied, Examples 1 to 2 in which a suitable pressure was applied to the cathode outlet exhibited higher Faraday efficiency and carbon dioxide conversion rate, and lower overvoltage than Comparative Examples 1 and 2, so it can be confirmed that the electrolysis efficiency of Examples 1 and 2 is superior thereto.
  • Comparative Example 1 exhibited the Faraday efficiency and the carbon dioxide conversion rate which are the same as those of Example 1, but had a higher overvoltage, so that it can be seen that the electrolysis efficiency of Comparative Example 1 was lower than that of Example 1.
  • Example 3 and Comparative Example 3 a current having a current density 200 mA/cm 2 was applied, and even in this case, it can be seen that the electrolysis efficiency of Example 3 in which a suitable pressure was applied to the cathode outlet was superior to that of Comparative Example 3 in which no pressure was applied.
  • Example 4 and Comparative Example 4 has the same increase in electrode area and cathode inlet flow rate, and even in this case, it can be seen that the electrolysis efficiency of Example 4 in which a suitable pressure was applied to the cathode outlet was superior to that of Comparative Example 4 in which no pressure was applied.

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