WO2020138668A1 - Batterie secondaire générant de l'hydrogène à l'aide de dioxyde de carbone et système de génération d'énergie complexe doté de cette dernière - Google Patents

Batterie secondaire générant de l'hydrogène à l'aide de dioxyde de carbone et système de génération d'énergie complexe doté de cette dernière Download PDF

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Publication number
WO2020138668A1
WO2020138668A1 PCT/KR2019/013460 KR2019013460W WO2020138668A1 WO 2020138668 A1 WO2020138668 A1 WO 2020138668A1 KR 2019013460 W KR2019013460 W KR 2019013460W WO 2020138668 A1 WO2020138668 A1 WO 2020138668A1
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Prior art keywords
electrolyte
secondary battery
carbon dioxide
electrolyte solution
reaction space
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PCT/KR2019/013460
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English (en)
Korean (ko)
Inventor
김건태
김창민
김정원
Original Assignee
울산과학기술원
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Priority claimed from KR1020180170838A external-priority patent/KR102042683B1/ko
Priority claimed from KR1020190007608A external-priority patent/KR102205629B1/ko
Priority claimed from KR1020190007609A external-priority patent/KR102163935B1/ko
Application filed by 울산과학기술원 filed Critical 울산과학기술원
Publication of WO2020138668A1 publication Critical patent/WO2020138668A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/673—Containers for storing liquids; Delivery conduits therefor
    • H01M50/682—Containers for storing liquids; Delivery conduits therefor accommodated in battery or cell casings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present technology relates to a secondary battery, and more particularly, to provide a secondary battery using carbon dioxide and a combined power generation system having the same.
  • Carbon dioxide emissions by industry type are highest in energy sources such as power plants, and carbon dioxide generated in the cement/steel/refining industry including power generation accounts for half of the world's emissions.
  • the CO2 conversion/utilization field can be largely divided into chemical conversion, biological conversion, and direct utilization, and the technical categories can be categorized into catalyst, electrochemistry, bioprocess, light utilization, inorganic (carbonation), and polymer.
  • Carbon dioxide is generated in various industries and processes, and various approaches for carbon dioxide reduction are required because carbon dioxide reduction cannot be achieved with one technology.
  • CCUS Carbon Capture & Storage
  • CCU CCU
  • CCUS technology is recognized as an effective method to reduce GHG emissions, but faces the problems of high investment cost, the possibility of releasing harmful capture agents into the atmosphere, and low technology maturity.
  • CCUS provides a means to substantially reduce greenhouse gas emissions, but there are many complements to the realization of technology. Accordingly, there is a need to develop a new concept of breakthrough technology that more efficiently captures, stores, and utilizes carbon dioxide.
  • Korean Patent Publication No. 10-2015-0091834 includes a liquid cathode part including a sodium-containing solution and a cathode impregnated in the sodium-containing solution; An anode portion including a liquid organic electrolyte, an anode impregnated with the liquid organic electrolyte, and a negative electrode active material positioned on the anode surface; And a solid electrolyte positioned between the cathode portion and the cathode portion. And a hydrogen discharge part connected to the cathode part to draw hydrogen generated in the cathode part to the outside during discharge.
  • the purpose of the present technology is to provide a secondary battery that produces hydrogen when discharged by using carbon dioxide, a greenhouse gas, as a raw material.
  • Another object of the present technology is to provide a secondary battery with improved discharge capacity while producing hydrogen upon discharge with the removal of carbon dioxide.
  • Another object of the present technology is to provide a secondary battery-metal recovery system capable of recovering metal used in the removal of carbon dioxide.
  • a secondary battery capable of charging and discharging, at least a first electrolyte that is an aqueous electrolyte accommodated in a first reaction space and the first electrolyte A cathode part having a cathode that is partially locked; And an anode portion including a second electrolyte, which is an aqueous electrolyte accommodated in the second reaction space, and an anode that is at least partially submerged in the second electrolyte, and in the discharge process, the temperature of the first electrolyte and the second electrolyte is It is maintained at 60°C to 80°C, carbon dioxide gas is introduced into the first electrolyte, and hydrogen ions and bicarbonate ions are generated by the reaction of water and the carbon dioxide gas in the first electrolyte, and the hydrogen ions and the cathode A secondary battery in which hydrogen gas is generated due to electrons being combined is provided.
  • a secondary battery capable of charging and discharging, at least a first electrolyte solution which is an aqueous electrolyte accommodated in a first reaction space and the first electrolyte solution A cathode part having a cathode that is partially locked; A carbon dioxide treatment unit having the first electrolyte solution accommodated in an accommodation space communicating with the first reaction space; And an anode portion including a second electrolyte, which is an aqueous electrolyte accommodated in the second reaction space, and an anode that is at least partially submerged in the second electrolyte, and in the discharge process, the temperature of the first electrolyte and the second electrolyte is It is maintained at 60°C to 80°C, carbon dioxide gas is introduced into the first electrolyte solution in the accommodation space, hydrogen ions and bicarbonate ions are generated by reaction of water and the carbon dioxide gas in the first electrolyte solution, and the ca
  • a secondary battery capable of charging and discharging, comprising: an electrolyte that is an aqueous electrolyte accommodated in a reaction space; A cathode immersed in at least a portion of the electrolyte solution; And an anode at least partially submerged in the electrolytic solution, and in the discharge process, the temperature of the electrolytic solution is maintained at 60°C to 80°C, carbon dioxide gas flows into the electrolyte solution, and the reaction of water and the carbon dioxide gas in the electrolyte solution Thereby, a hydrogen ion and bicarbonate ion are generated, and a secondary battery in which hydrogen gas is generated by combining electrons of the hydrogen ion and the cathode is provided.
  • the aqueous electrolyte contained in the reaction space and the receiving space communicating with the reaction space is an electrolyte;
  • an anode in which at least a part is immersed in the electrolyte in the reaction space, and in the discharge process the temperature of the electrolyte is maintained at 60°C to 80°C, and carbon dioxide gas is introduced into the electrolyte in the receiving space, whereby Hydrogen ions and bicarbonate ions are generated by the reaction of water and the carbon dioxide gas, and in the reaction space, hydrogen ions and electrons of the cathode are combined to generate hydrogen gas, and carbon dioxide flowing into the aqueous electrolyte in the accommodation space
  • a secondary battery is provided in which non-ionized carbon dioxide gas in the gas is separated from the electrolyte in the
  • the first electrolyte and the first electrolyte which are aqueous electrolytes accommodated in the first reaction space, A cathode part having a cathode at least partially locked;
  • An anode unit including a second electrolyte solution that is an aqueous electrolyte accommodated in a second reaction space, and an anode at least partially submerged in the second electrolyte solution;
  • an electrolyte circulating unit comprising a second electrolyte solution stored in an electrolyte storage space communicating with the second reaction space, and a circulation pump circulating the second electrolyte solution between the electrolyte storage space and the second reaction space.
  • carbon dioxide gas is introduced into the first electrolyte solution, and hydrogen ions and bicarbonate ions are generated by reaction of water and the carbon dioxide gas in the first electrolyte solution, and electrons of the hydrogen ion and the cathode are combined to generate hydrogen.
  • a secondary battery in which gas is generated is provided.
  • the first electrolyte and the first electrolyte which are aqueous electrolytes accommodated in the first reaction space, A cathode part having a cathode at least partially locked; A carbon dioxide treatment unit having the first electrolyte solution accommodated in an accommodation space communicating with the first reaction space; An anode unit including a second electrolyte solution that is an aqueous electrolyte accommodated in a second reaction space, and an anode at least partially submerged in the second electrolyte solution; And an electrolyte circulating unit having a circulating pump for circulating the second electrolyte between the electrolyte storage space and the second reaction space, and an electrolyte storage space in which the second electrolyte is stored, and Carbon dioxide gas is introduced into the first electrolytic solution, and hydrogen ions and bicarbonate ions are generated by the reaction of water and the carbon dioxide gas in
  • a secondary battery is provided in which gas is generated, and the carbon dioxide processing unit separates non-ionized carbon dioxide gas from the first electrolyte from among the carbon dioxide gas flowing into the first electrolyte in the accommodation space so as not to be supplied to the cathode.
  • the secondary battery for generating hydrogen by using carbon dioxide as a fuel in the discharge process;
  • a reformer for producing hydrogen-rich reformed gas from hydrogen-containing fuel and generating carbon dioxide as a by-product;
  • a fuel cell receiving the reformed gas produced from the reformer as fuel;
  • a carbon dioxide supply unit supplying carbon dioxide generated in the reformer to the secondary battery.
  • the secondary battery for generating hydrogen by using carbon dioxide as a fuel in the discharge process;
  • a reformer producing a reforming gas rich in hydrogen from a hydrogen-containing furnace;
  • a fuel cell receiving the reformed gas produced from the reformer as fuel;
  • a hydrogen supply unit that additionally supplies hydrogen generated in the secondary battery as fuel of the fuel cell.
  • a secondary battery for generating hydrogen by using carbon dioxide as a fuel in the discharge process;
  • a reformer for producing hydrogen-rich reformed gas from hydrogen-containing fuel and generating carbon dioxide as a by-product;
  • a fuel cell receiving the reformed gas produced from the reformer as fuel;
  • a carbon dioxide supply unit supplying carbon dioxide generated in the reformer to the secondary battery;
  • a hydrogen supply unit that additionally supplies hydrogen generated in the secondary battery as fuel of the fuel cell.
  • the secondary battery is a first electrolyte that is an aqueous electrolyte accommodated in the first reaction space, and the agent 1 Cathode portion having a cathode at least partially submerged in the electrolyte;
  • an anode unit including a second electrolyte, which is an aqueous electrolyte accommodated in a second reaction space, and an anode that is at least partially submerged in the second electrolyte, wherein carbon dioxide gas is introduced into the first electrolyte, and the first Hydrogen ions and bicarbonate ions are generated by the reaction of water in the electrolyte with the carbon dioxide gas, and hydrogen ions are generated by combining the hydrogen ions and the electrons of the cathode, and the metal recovery part dissolves metal ions oxidized at the anode.
  • a supply unit that receives the second electrolyte solution; A recovery space accommodating the supplied second electrolyte; A second cathode made of the same material as the anode at least partially immersed in the second electrolyte contained in the recovery space; a second anode immersed in the second electrolyte contained in the recovery space; And a power supply unit supplying power to the second cathode and the second anode.
  • a secondary battery-metal recovery system is provided for recovering oxidized metal ions from the supplied second electrolyte.
  • the secondary battery is an electrolyte that is an aqueous electrolyte accommodated in the reaction space; A cathode immersed in at least a portion of the electrolyte solution; And an anode in which at least a part is immersed in the electrolyte solution, carbon dioxide gas is introduced into the electrolyte solution, hydrogen ions and bicarbonate ions are generated by reaction of water and the carbon dioxide gas in the electrolyte solution, and the hydrogen ions and the cathode Hydrogen gas is generated by the electrons being combined, and the metal recovery part is a supply part receiving an electrolyte solution in which metal ions oxidized at the anode are dissolved; A recovery space accommodating the supplied electrolyte solution; A second cathode made of the same material as the anode, at least partially immersed in the electrolyte solution accommodated in the recovery space; a second ano
  • the present technology it is possible to achieve all the objects of the present technology described above. Specifically, it includes a cathode and a metal anode immersed in the electrolyte, which is an aqueous electrolyte, and the temperature of the electrolyte in the secondary battery generating hydrogen gas by introducing carbon dioxide gas into the electrolyte during the discharge process has a maximum current density of about twice the room temperature.
  • the optimum temperature of 60°C to 80°C the performance of the secondary battery and the combined power generation system including the secondary battery is greatly improved.
  • the second electrolytic solution accommodated in the second reaction space is circulated by the electrolyte circulating portion, thereby slowing corrosion of the anode metal in the second reaction space, and washing the metal oxide that has been corroded and accumulated on the surface of the anode metal, thereby discharging the discharge capacity. It is greatly increased.
  • FIG. 1 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to an embodiment of the present technology.
  • FIG. 2 is a graph showing the results of a half-cell experiment according to the temperature of the electrolyte solution for the secondary battery of the embodiment shown in FIG.
  • FIG. 3 is a graph showing HER initiation regions by temperature in the graph of FIG. 2.
  • FIG. 4 is a graph showing HER voltage for each temperature at a current density of 10 mA/cm 2 in the graph of FIG. 2.
  • FIG. 5 is a graph showing the results of a single cell experiment according to the temperature of the electrolyte for the secondary battery of the embodiment shown in FIG.
  • FIG. 6 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 7 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 8 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 9 is a schematic view showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 10 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 11 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 12 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen by using carbon dioxide according to another embodiment of the present technology.
  • FIG. 13 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 14 is a view showing a schematic configuration of a complex power generation system having a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • 15 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • 16 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • 17 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • FIG. 18 is a schematic diagram showing a discharge state of a secondary battery that produces hydrogen using carbon dioxide according to another embodiment of the present technology.
  • 19 is a schematic diagram showing a discharge state of a secondary battery for producing hydrogen using carbon dioxide according to another embodiment of the present technology.
  • 20 is a schematic diagram of a metal recovery part of a secondary battery-metal recovery system according to another embodiment of the present technology.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, and a connection unit 190 connecting the cathode unit 110 and the anode unit 150.
  • the secondary battery 100 uses the carbon dioxide gas (CO 2 ), which is a greenhouse gas, as a raw material in the discharge process to produce hydrogen (H 2 ), which is an eco-friendly fuel.
  • CO 2 carbon dioxide gas
  • H 2 hydrogen
  • the cathode unit 110 includes a first reaction vessel 110a that provides a first reaction space 111 therein, a first electrolyte 115 that is an aqueous electrolyte contained in the first reaction space 111, and a first A cathode 118 in which at least a portion is immersed in the electrolyte 115 is provided.
  • a first electrolyte 115 an alkaline aqueous solution (in this embodiment, an elution of CO 2 in a strong basic solution of 1M KOH is used), seawater, tap water, distilled water, and the like can be used.
  • the temperature of the first electrolyte 115 is preferably 60°C to 70°C, and most preferably 70°C.
  • the cathode 118 is an electrode for forming an electrical circuit, and may be carbon paper, carbon fiber, carbon felt, carbon cloth, metal foam, metal thin film, or a combination thereof, and a platinum catalyst may also be used.
  • a platinum catalyst may also be used.
  • all other catalysts that can be generally used as a hydrogen generation reaction (HER) catalyst such as a carbon-based catalyst, a carbon-metal-based composite catalyst, and a perovskite oxide catalyst, are also included.
  • HER hydrogen generation reaction
  • a first inlet port 112, a first outlet port 113, and a first connector port 114 communicating with the first reaction space 111 are formed in the first reaction container 110a.
  • the first inlet 112 is positioned below the first reaction space 111 so that it is located below the water surface of the first electrolyte 115.
  • the first outlet 113 is positioned above the first reaction space 111 so as to be positioned above the water surface of the first electrolyte 115.
  • Carbon dioxide which is used as a raw material in the discharge process, is introduced into the first reaction space 111 through the first inlet 112, and the first electrolyte 115 may also be introduced, if necessary.
  • Gas generated in the process of charging and discharging is discharged to the outside through the first outlet 113.
  • the first inlet 112 and the first outlet 113 may be selectively opened and closed in a timely manner by a valve or the like during charging and discharging.
  • the first connector 114 is positioned below the water surface of the first electrolyte 115, and the connection part 190 is connected to the first connector 114. In the cathode unit 110, a carbon dioxide elution reaction occurs in the discharge process.
  • the anode unit 150 includes a second reaction vessel 150a providing a second reaction space 151 therein, a second electrolyte 155 serving as an aqueous electrolyte contained in the second reaction space 151, and a second An anode 158 in which at least a portion is immersed in the electrolyte 155 is provided.
  • a second electrolyte solution 155 an alkali solution having a high concentration is used, for example, 1M KOH or 6M KOH may be used.
  • the temperature of the second electrolyte 155 is preferably 60°C to 80°C, and most preferably 70°C.
  • the anode 158 is an electrode of a metal material constituting an electrical circuit, and in this embodiment, it will be described that zinc (Zn) or aluminum (Al) is used as the anode 158.
  • an alloy containing zinc or aluminum may be used as the anode 158.
  • vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) may be used as the anode 158, wherein the acid or basic
  • the solution may be used as the second electrolyte 155.
  • a second connector 154 communicating with the second reaction space 151 is formed in the anode unit 150. The second connector 154 is positioned below the water surface of the second electrolyte 155, and the connection unit 190 is connected to the second connector 154.
  • connection part 190 includes a connection passage 191 connecting the cathode part 110 and the anode part 150, and an ion transfer member 192 installed inside the connection passage 191.
  • connection passage 191 extends between the first connector 114 formed in the cathode portion 110 and the second connector 154 formed in the anode portion 150 so that the first reaction space 111 of the cathode portion 110 ) And the second reaction space 151 of the anode 150 are communicated.
  • the ion transfer member 192 is installed inside the connection passage 191.
  • the ion transfer member 192 is generally disk-shaped and is installed in a form of blocking the inside of the connection passage 191.
  • the ion transfer member 192 is made of a porous structure and allows only the movement of ions between the cathode portion 110 and the anode portion 150.
  • the material of the ion transfer member is described as glass, but the present technology is not limited thereto, and other materials having a porous structure may also be used, and this is also within the scope of the present technology.
  • the ion transfer member 192 has a pore size of 40 to 90 microns corresponding to a G2 grade (grade), 15 to 40 microns corresponding to a G3 grade, 5 to 15 microns corresponding to a G4 grade, Porous glass of 1 to 2 microns corresponding to G5 can be used.
  • the ion transfer member 192 eliminates ion imbalance generated in the discharge process by transferring only ions.
  • FIG. 1 shows the discharge process of the secondary battery 100 together.
  • carbon dioxide gas is injected into the first electrolyte 115 through the first inlet 112, and a chemical elution reaction of carbon dioxide is performed in the cathode 110 as shown in [Scheme 1].
  • the carbon dioxide gas (CO 2 ) supplied to the cathode portion 110 undergoes a spontaneous chemical reaction with water (H 2 O) of the first electrolyte 115 and hydrogen cations (H + ) and bicarbonate (HCO 3 -) is generated.
  • the anode 158 is aluminum (Al)
  • an oxidation reaction as shown in [Reaction Scheme 6] is performed.
  • FIG. 2 is a graph showing the results of a half-cell test according to the temperature of the electrolytes 115 and 155 for the secondary battery of the embodiment shown in FIG. 1, and FIG. 3 discloses HER (hydrogen generation reaction) by temperature in the graph of FIG. 2 It is a graph showing the region, and FIG. 4 is a graph showing HER voltage for each temperature at a current density of 10 mA/cm 2 in the graph of FIG. 2.
  • the HER initiation region improves from room temperature (RT) to 45°C as the temperature increases, and tends to decrease gradually after 45°C.
  • the performance improves as the temperature increases from room temperature (RT), but tends to be saturated from 60°C.
  • FIG. 5 is a graph showing the results of a single cell experiment according to the temperature of the electrolytes 115 and 155 for the secondary battery of the embodiment shown in FIG. 1. Referring to FIG. 5, it is confirmed that in the case of the cathode voltage in which the hydrogen generation reaction occurs, the tendency similar to the half cell performance results shown in FIGS. 2 to 4 is shown. In the case of the anode voltage in which the oxidation reaction occurs, the oxidation result is improved due to the temperature increase, and it is confirmed that the electrode oxidation performance is saturated in the temperature range of 70°C to 80°C.
  • the cathode and the anode exhibits excellent performance in the temperature range of the electrolyte at 60°C to 80°C, and the maximum current density at a temperature of 70°C is about 320mA/cm2, at room temperature. It is confirmed that it shows the best performance by increasing about 2 times to about 160 mA/cm 2 measured. This is because the rate of the hydrogen generation reaction and the metal oxidation reaction is accelerated at the above temperature, and at a temperature exceeding 80° C., the rate of carbon dioxide dissolution reaction is slowed down, and the amount of dissolution is small, so performance decreases.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, a connection unit 190 connecting the cathode unit 110 and the anode unit 150, and a carbon dioxide processing unit 120 ), the carbon dioxide circulation supply unit 130, and the cathode 110 and the carbon dioxide processing unit 120, the communication pipe 140 for communicating.
  • the cathode unit 110, the anode unit 150, and the connection unit 190 are the same as those described in the embodiment illustrated in FIG. 1, so a detailed description thereof will be omitted.
  • the secondary battery 100 of the configuration shown in FIG. 6 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably 70° C., as described through FIGS. 2 to 5. Is done.
  • the carbon dioxide processing unit 120 includes a storage container 120a that provides a storage space 121 therein, and a first that is accommodated in the storage space 121 and is the same electrolyte solution as the first electrolyte solution 115 of the cathode 110.
  • An electrolyte 115 is provided.
  • the receiving container 120a is located at the upper portion of the receiving space 121, the second inlet 122 through which carbon dioxide gas flows into the receiving space 121, the communication port 123 to which the connecting pipe 140 is connected, and the receiving space 121.
  • the second outlet 124 is formed.
  • the second inlet 122 is positioned above the communication port 123 in the accommodation space 121, and is located below the water surface of the second outlet 124 and the first electrolyte 115. Carbon dioxide gas used as a raw material in the discharge process is introduced into the receiving space 121 through the second inlet 122.
  • the first electrolyte 115 may also be supplied as needed through the second inlet 122.
  • the second inlet 122 and the first outlet 113 may be selectively opened and closed at appropriate times by a valve or the like during charging and discharging.
  • the communication port 123 is located below the second inlet port 122 in the accommodation space 121, and a connection pipe 140 is connected to the communication port 123.
  • the accommodation space 121 communicates with the first reaction space 111 through the communication port 123.
  • the second outlet 124 is positioned above the water surface of the second inlet 122 and the first electrolyte 115 in the accommodation space 121. Carbon dioxide gas that is not ionized because it is not dissolved in the first electrolyte 115 in the accommodation space 121 is discharged to the outside through the second outlet 124. The carbon dioxide gas discharged through the second outlet 124 is supplied to the second inlet 122 through the carbon dioxide circulation supply unit 130.
  • the carbon dioxide circulation supply unit 130 recirculates the carbon dioxide gas discharged through the second outlet 224 to the second inlet 122 to re-supply it.
  • the connector 140 connects the first inlet port 112 of the first reaction space 111 and the communication port 123 of the receiving space 121.
  • the first reaction space 111 and the accommodation space 121 communicate with each other through a connection passage 141 formed inside the connection pipe 140.
  • Carbon dioxide gas that is not ionized because it is not dissolved in the first electrolyte 115 among the carbon dioxide introduced into the accommodation space 121 of the carbon dioxide processing unit 120 through the second inlet 122 is the first reaction space of the cathode 110
  • the carbon dioxide gas discharged through the second outlet 124 and discharged through the second outlet 124 after being collected in the space above the water surface of the first electrolyte 115 in the accommodation space 121 without being able to move to (111) Is supplied to the receiving space 121 through the second inlet 122 by the carbon dioxide circulation supply unit 130 is recycled.
  • carbon dioxide gas that is not ionized because it is not dissolved in the first electrolyte 115 among the carbon dioxide introduced into the accommodation space 121 of the carbon dioxide processing unit 120 does not move to the first reaction space 111 of the cathode 110. Since it is not possible, high-purity hydrogen in which carbon dioxide is not mixed may be discharged through the first outlet 113.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, and a connection unit 190 connecting the cathode unit 110 and the anode unit 150.
  • the secondary battery 100 of the configuration shown in FIG. 7 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably at a temperature of 70° C., as described through FIGS. 2 to 5. do.
  • the cathode 110 includes a first reaction vessel 110a that provides a first reaction space 111 therein, a first electrolyte 115 contained in the first reaction space 111, and a first electrolyte 115 ) Is provided with a cathode (118) at least partially submerged.
  • a first electrolyte solution 115 an aqueous potassium hydroxide solution (in this embodiment, an elution of CO 2 in a strong basic solution of 1M KOH is used) is used. Since the configuration of the first reaction vessel 110a and the cathode 118 is the same as the corresponding configuration in the embodiment illustrated in FIG. 1, detailed description thereof will be omitted.
  • the anode unit 150 includes a second reaction container 150a providing a second reaction space 151 therein, a second electrolyte solution 155 contained in the second reaction space 151, and a second electrolyte solution 155 ) Is provided with an anode 158 in which at least a part is locked.
  • a second electrolyte solution 155 an aqueous potassium hydroxide solution is described, and for example, 1M KOH or 6M KOH may be used. Since the configuration of the second reaction vessel 150a and the anode 158 is the same as the corresponding configuration in the embodiment illustrated in FIG. 1, detailed description thereof will be omitted.
  • connection part 190 includes a connection passage 191 connecting the cathode part 110 and the anode part 150, and an ion exchange membrane 292 installed inside the connection passage 191.
  • connection passage 191 has the same configuration as the connection passage 191 illustrated in FIG. 1, and an ion exchange membrane 192 is installed inside the connection passage 191.
  • the ion exchange membrane 192 is installed in a form that blocks the inside of the connection passage 191.
  • the ion exchange membrane 192 allows only the movement of ions between the cathode portion 110 and the anode portion 150.
  • the potassium ion (K + ) contained in the second electrolyte solution 155 is moved to the first electrolyte solution 115 by the ion exchange membrane 192.
  • a fluorine resin-based cation exchange membrane developed by DuPont, USA is used to describe that Nafion is used, but the present technology is not limited thereto, and potassium ion ( Anything that allows only the movement of K + ) is possible.
  • the ion exchange membrane 192 eliminates ion imbalance generated in the discharge process by transferring only ions.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, a connection unit 190 connecting the cathode unit 110 and the anode unit 150, and a carbon dioxide processing unit 120 ), the carbon dioxide circulation supply unit 130, and the cathode 110 and the carbon dioxide processing unit 120, the communication pipe 140 for communicating.
  • the cathode unit 110, the anode unit 150, and the connection unit 190 are the same as those described in the embodiment shown in FIG. 7, and the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit 130, and the connection pipe 140 are Since it is the same as the corresponding configuration shown in FIG.
  • the secondary battery 100 of the configuration shown in FIG. 8 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably 70° C., as described through FIGS. 2 to 5. do.
  • the configuration of reference numerals not described in FIG. 8 is the same as the configuration indicated by the same reference numerals in the embodiment illustrated in FIG. 6.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, a connection unit 190 connecting the cathode unit 110 and the anode unit 150.
  • the cathode unit 110 and the anode unit 250 are the same as the corresponding components of the embodiment illustrated in FIG. 7, so a detailed description thereof will be omitted.
  • the secondary battery 100 of the configuration shown in FIG. 9 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably at a temperature of 70° C., as described through FIGS. 2 to 5. do.
  • connection part 190 includes a connection passage 191 connecting the cathode part 110 and the anode part 150 and an ion exchange membrane 192 installed inside the connection passage 191.
  • connection passage 191 is the same as the connection passage 191 of the embodiment shown in FIG. 7, and an ion exchange membrane 192 is installed inside the connection passage 191.
  • the ion exchange membrane 192 is installed in a form that blocks the inside of the connection passage 191.
  • the ion exchange membrane 192 allows only the movement of ions between the cathode portion 110 and the anode portion 150.
  • the hydroxide ions contained in the first electrolyte solution (115) (OH -) is moved in the second electrolyte 155.
  • a fluorine resin-based cation exchange membrane Nafion developed by DuPont of the United States is used, but the present technology is not limited thereto, and hydroxide ions ( all as long as it is possible that only) movement of the - OH.
  • Hydroxide ions by an ion exchange membrane (192) (OH -) is written doemeu delivered from the cathode 110 to the anode 150, thereby eliminating the ion imbalance caused in the discharge process.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, a connection unit 190 connecting the cathode unit 110 and the anode unit 150, and a carbon dioxide processing unit 120 ), the carbon dioxide circulation supply unit 130, and the cathode 110 and the carbon dioxide processing unit 120, the communication pipe 140 for communicating.
  • the cathode unit 110, the anode unit 150, and the connection unit 190 are the same as those described in the embodiment shown in FIG. 9, and the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit 130, and the connection pipe 140 are Since it is the same as the corresponding configuration shown in FIG.
  • the secondary battery 100 of the configuration shown in FIG. 10 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably 70° C., as described through FIGS. 2 to 5. do.
  • the configuration of reference numerals not described in FIG. 10 is the same as the configuration indicated by the same reference numerals in the embodiment illustrated in FIG. 8.
  • a salt bridge connecting the first electrolyte 115 and the second electrolyte 155 may be used instead of the connecting portion 190, which is also within the scope of the present technology. Belong.
  • a salt bridge an internal solution of a salt bridge that is commonly used, such as potassium chloride (KCl) or sodium chloride (NaCl), may be used as the internal solution of the salt bridge.
  • KCl potassium chloride
  • NaCl sodium chloride
  • HCO 3 ⁇ bicarbonate ions
  • sodium ions are diffused from the salt bridge and exist as ions in the form of an aqueous sodium hydrogen carbonate (NaHCO 3 ) solution.
  • NaHCO 3 aqueous sodium hydrogen carbonate
  • the secondary battery 100 includes a reaction vessel 210 providing a reaction space 211 therein, an electrolyte 215 serving as an aqueous electrolyte contained in the reaction space 211, and a reaction space 211.
  • the cathode 118 is immersed in the electrolyte 215, and the anode 158 is immersed in the electrolyte 215 in the reaction space 211.
  • the secondary battery 100 uses the carbon dioxide gas (CO 2 ), which is a greenhouse gas, as a raw material in the discharge process to produce hydrogen (H 2 ), which is an eco-friendly fuel.
  • CO 2 carbon dioxide gas
  • H 2 hydrogen
  • the reaction vessel 210 provides a reaction space 211 in which the electrolyte 215 is contained and the cathode 118 and the anode 158 are accommodated.
  • a first inlet 212 and a first outlet 213 in communication with the reaction space 211 are formed in the reaction vessel 210.
  • the first inlet 212 is positioned below the reaction space 211 to be positioned below the water surface of the electrolyte 215.
  • the first outlet 213 is positioned above the reaction space 211 so as to be positioned above the water surface of the electrolyte 215.
  • Carbon dioxide gas used as a raw material in the discharge process is introduced into the reaction space 211 through the first inlet 212, and an electrolyte 215 may also be introduced if necessary.
  • Gas generated in the process of charging and discharging is discharged to the outside through the first outlet 213.
  • the first inlet 212 and the first outlet 213 may be selectively opened and closed in a timely manner by a valve or the like during charging and discharging.
  • carbon dioxide elution reaction occurs in the discharge process.
  • a basic solution or seawater is used as the electrolyte 115.
  • the electrolytic solution 215 becomes weakly acidic by the carbon dioxide gas flowing through the first inlet 212 during the discharge process.
  • the cathode 118 is at least partially immersed in the electrolyte 215 in the reaction space 211.
  • the cathode 118 is positioned relatively closer to the first inlet 212 than the anode 158 in the reaction space 211.
  • the cathode 118 is an electrode for forming an electrical circuit, and may be carbon paper, carbon fiber, carbon felt, carbon cloth, metal foam, metal thin film, or a combination thereof, and a platinum catalyst may also be used.
  • HER hydrogen generation reaction
  • a reduction reaction occurs at the cathode 118, and hydrogen is generated accordingly.
  • the anode 158 is at least partially immersed in the electrolyte 215 in the reaction space 211.
  • the anode 158 is located relatively far from the first inlet 212 in the reaction space 211 than the cathode 118.
  • the anode 158 is an electrode of a metal material constituting an electrical circuit, and in this embodiment, as the anode 158, vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel It is explained that (Ni), copper (Cu), aluminum (Al) or zinc (Zn) is used.
  • an oxidation reaction occurs in the anode 158 according to the weakly acidic environment.
  • the secondary battery 100 of the configuration shown in FIG. 11 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably 70° C., as described through FIGS. 2 to 5. Is done.
  • FIG. 11 shows the discharge process of the secondary battery 100 together.
  • carbon dioxide gas is injected into the electrolyte solution 215 through the first inlet 212 during discharge, and a chemical elution reaction of carbon dioxide as in [Reaction Scheme 1] is performed in the reaction space 211. That is, carbon dioxide (CO 2 ) supplied to the reaction space 211 generates hydrogen cations (H + ) and bicarbonate (HCO 3 ⁇ ) through spontaneous chemical reactions with water (H 2 O) of the electrolyte 215.
  • an electrical reaction such as [Scheme 2] is performed at the cathode 118. That is, hydrogen cations (H + ) in the vicinity of the cathode 118 receive electrons (e ⁇ ) from the cathode 118 to generate hydrogen (H 2 ) gas. The generated hydrogen (H 2 ) gas is discharged to the outside through the first outlet 213.
  • the secondary battery 100 includes a reaction vessel 210 that provides a reaction space 211 therein, an electrolyte solution 215 contained in the reaction space 211, and an electrolyte solution in the reaction space 211 ( Cathode 118 at least partially immersed in 215, anode 158 at least partially immersed in electrolyte 215 in reaction space 211, carbon dioxide processing unit 120, and carbon dioxide circulation supply unit 130, and a connection pipe 140 for connecting the reaction vessel 210 and the carbon dioxide treatment unit 120.
  • the reaction vessel 210, the electrolyte 215, the cathode 118, and the anode 158 are the same as each of the corresponding configurations described in the embodiment shown in FIG. 11, and the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit ( 130) and the connector 140 is the same as each of the corresponding components shown in FIG. 6, so a detailed description thereof will be omitted.
  • the secondary battery 100 of the configuration shown in FIG. 12 also preferably exhibits excellent performance at a temperature range of 60° C. to 80° C., more preferably 70° C., as described through FIGS. 2 to 5. Is done.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, an electrolyte circulation unit 180 connected to the anode unit 150, a cathode unit 110, and an anode unit It includes a connecting portion 190 for connecting the (150).
  • the secondary battery 100 uses the carbon dioxide gas (CO 2 ), which is a greenhouse gas, as a raw material in the discharge process to produce hydrogen (H 2 ), which is an eco-friendly fuel.
  • CO 2 carbon dioxide gas
  • the cathode unit 110, the anode unit 150, and the connection unit 190 are the same as the corresponding components in the embodiment illustrated in FIG. 1, so a detailed description thereof will be omitted.
  • the anode 158 is formed with a first through hole 1581 and a second through hole 1582 passing through the anode 158.
  • the first electrolyte 155 supplied from the electrolyte circulation unit 180 flows into the second reaction space 151 through the first through hole 1561, and the second reaction through the second through hole 1582.
  • the second electrolyte 155 in the space 151 is discharged to the electrolyte circulation unit 180.
  • a second connector 154 communicating with the second reaction space 151 is formed in the anode unit 150.
  • the electrolyte circulating portion 180 circulates the second electrolyte 155 used in the anode portion 150.
  • the electrolyte circulation unit 180 includes an electrolyte storage container 182 and an electrolyte storage space 181 that provide an electrolyte storage space 181 in which the second electrolyte 155 used in the anode 150 is stored.
  • the first circulation pipe 184 and the second circulation pipe 185 communicating with the second reaction space 151 of the anode 150 and the electrolyte storage space 181 and the second reaction space 151 are removed.
  • 2 is provided with a circulation pump 188 for flowing the second electrolyte 155 so that the electrolyte 155 circulates.
  • the electrolyte storage container 182 provides an electrolyte storage space 181 therein, and a second electrolyte 155 used in the anode unit 150 is stored in the electrolyte storage space 181.
  • the electrolyte storage space 181 communicates with the second reaction space 151 of the anode unit 150 through the first circulation pipe 184 and the second circulation pipe 185.
  • the second electrolyte 155 stored in the electrolyte storage space 181 is supplied to the second reaction space 151 through the first circulation tube 184.
  • the second electrolyte 155 stored in the second reaction space 151 flows through the second circulation pipe 185 into the electrolyte storage space 181.
  • the first circulation pipe 184 communicates the electrolyte storage space 181 and the second reaction space 151.
  • the second electrolyte 155 stored in the electrolyte storage container 182 flows through the first circulation pipe 184 to the second reaction space 151.
  • the first circulation pipe 184 is directly connected to the first through hole 1581 formed in the anode 158 in the second reaction space 151. Accordingly, the second electrolyte 155 flowing through the first circulation pipe 184 from the electrolyte storage space 181 is discharged to the second reaction space 151 through the first through hole 1581.
  • the second circulation pipe 185 communicates the electrolyte storage space 181 and the second reaction space 151.
  • the second electrolyte 155 stored in the second reaction space 151 flows through the second circulation pipe 185 to the electrolyte storage container 182.
  • the second circulation pipe 185 is directly connected to the second through hole 1582 formed in the anode 158 in the second reaction space 151. Accordingly, the second electrolyte solution 155 of the second reaction space 151 flows through the second through hole 1582 of the anode 158 and the second circulation tube 185 in sequence to the electrolyte storage container 182. do.
  • the circulation pump 188 flows the second electrolyte 155 such that the second electrolyte 155 circulates between the electrolyte storage space 181 and the second reaction space 151.
  • the circulation pump 188 is described as being installed in the first circulation pipe 184.
  • the second circulation pipe 185 may be installed at another suitable location, which is also within the scope of the present technology. Belong.
  • the combined power generation system 1000 includes a secondary battery 100 that generates hydrogen gas (H 2 ) using carbon dioxide gas (CO 2 ) as a raw material during a discharge process, A reformer 400 for producing hydrogen-rich reformed gas from hydrogen-containing fuel and additionally generating carbon dioxide gas (CO 2 ), a fuel cell 300 for producing electricity using hydrogen and oxygen, and a reformer 400 ) Produced by the carbon dioxide supply unit 500 for supplying the carbon dioxide gas generated in the secondary battery 100, the hydrogen supply unit 600 for supplying hydrogen gas generated in the secondary battery 100 to the fuel cell, and the reformer 400 It includes a reforming gas supply unit 700 for supplying the reformed gas to the fuel cell 300.
  • H 2 hydrogen gas
  • CO 2 carbon dioxide gas
  • CO 2 carbon dioxide gas
  • a fuel cell 300 for producing electricity using hydrogen and oxygen
  • a reformer 400 Produced by the carbon dioxide supply unit 500 for supplying the carbon dioxide gas generated in the secondary battery 100, the hydrogen supply unit 600 for supplying hydrogen gas generated in the secondary battery 100 to the fuel cell, and
  • the secondary battery 100 is a secondary battery 100 previously described with reference to FIG. 1, and uses carbon dioxide gas as a raw material in the discharge process and generates hydrogen gas as described in detail with reference to FIG. 1.
  • the carbon dioxide gas supplied to the secondary battery 100 is carbon dioxide gas generated from the reformer 400 and supplied through the carbon dioxide supply unit 500.
  • the hydrogen gas generated in the secondary battery 100 is supplied to the fuel cell 300 by the hydrogen supply unit 600.
  • the secondary battery 100 illustrated in FIG. 1 is described as being used in a combined power generation system, but unlike this, the secondary batteries of the embodiments illustrated in FIGS. 6 to 13 may be used, which is also the scope of the present technology. It belongs to.
  • the reformer 400 produces hydrogen-rich reformed gas from the hydrogen-containing fuel and additionally generates carbon dioxide gas.
  • the reformer 400 is described as a methane-steam reformer that produces hydrogen (H 2 ) by a reforming reaction of methane (CH 4 ) and water vapor (H 2 O).
  • the methane-steam reformer 400 occupies a considerable portion of the hydrogen production process because of the advantages of low process cost and mass production.
  • the following [Scheme 8] relates to the reforming reaction of the methane-steam reformer 400.
  • hydrogen produced in the methane-steam reformer 400 is supplied to the fuel, such as the fuel cell 300, by the reforming gas supply unit 700.
  • the methane-steam reformer 400 has many of the above-mentioned advantages, but as can be seen from [Scheme 8], it is necessary to supply water vapor from the outside for the operation of the process, and global warming as a by-product of hydrogen production. There is a problem that carbon dioxide, which is a main cause of environmental problems, is forced to be generated.
  • carbon dioxide generated from the methane-steam reformer 400 is discharged into the atmosphere or transferred to a separate carbon dioxide capture and storage process, instead of being supplied to the carbon dioxide supply unit 500 for the discharge reaction of the secondary battery 100
  • a system for linking the secondary battery 100 and the methane-steam reformer 400 can be solved as well as solving the problem of generating carbon dioxide, which is a necessary evil in the operation of the methane-steam reformer 400.
  • duplicate process can be omitted. Since the methane-steam reformer 400 is a known technique, detailed description thereof is omitted here.
  • the fuel cell 300 water is generated by a chemical reaction between hydrogen and oxygen, and electric energy is generated.
  • the fuel cell 300 has many advantages in terms of eco-friendliness, but must be supplied with hydrogen extracted from the methane-steam reformer 400 and the like.
  • the fuel cell 300 is constructed as one system with the secondary battery 100, so that hydrogen gas generated in the process of discharging the secondary battery 100 is supplied, so that efficiency can be significantly improved. .
  • the carbon dioxide supply unit 500 supplies carbon dioxide gas generated as a by-product in the reformer 400 to the secondary battery 100.
  • the hydrogen supply unit 600 supplies hydrogen gas generated as a by-product in the discharge process of the secondary battery 100 as fuel of the fuel cell 300.
  • the reforming gas supply unit 700 supplies the reformed gas produced by the reformer 400 as fuel of the fuel cell 300.
  • 15 to 21 show configurations for each of the secondary batteries that can be used in the system of FIG. 21 in place of the secondary battery 100 of the embodiment shown in FIG. 13.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, an electrolyte circulation unit 180 connected to the anode unit 150, a cathode unit 110, and an anode unit It includes a connecting portion 190 for connecting the 150, the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit 130, the cathode 110 and the connection pipe 140 for communicating the carbon dioxide processing unit 120.
  • the cathode unit 110, the anode unit 150, the electrolyte circulation unit 180, and the connection unit 190 are the same as those described in the embodiment illustrated in FIG. 13, and thus detailed description thereof will be omitted.
  • the carbon dioxide processing unit 120 is made of a storage container 120a that provides a storage space 121 therein, and an agent that is accommodated in the storage space 121 and is the same as the first electrolyte solution 115 of the cathode 110. 1
  • the electrolyte 115 is provided.
  • the receiving container 120a is located at the upper portion of the receiving space 121, the second inlet 122 through which carbon dioxide gas flows into the receiving space 121, the communication port 123 to which the connecting pipe 140 is connected, and the receiving space 121.
  • the second outlet 124 is formed.
  • the second inlet 122 is positioned above the communication port 123 in the accommodation space 121, and is located below the water surface of the second outlet 124 and the first electrolyte 115. Carbon dioxide gas used as a raw material in the discharge process is introduced into the receiving space 121 through the second inlet 122.
  • the first electrolyte 115 may also be supplied as needed through the second inlet 122.
  • the second inlet 122 and the first outlet 113 may be selectively opened and closed at appropriate times by a valve or the like during charging and discharging.
  • the communication port 123 is located below the second inlet port 122 in the accommodation space 121, and a connection pipe 140 is connected to the communication port 123.
  • the accommodation space 121 communicates with the first reaction space 111 through the communication port 123.
  • the second outlet 124 is positioned above the water surface of the second inlet 122 and the first electrolyte 115 in the accommodation space 121. Carbon dioxide gas that is not ionized because it is not dissolved in the first electrolytic solution 115 in the receiving space 121 is discharged to the outside through the second outlet 124. The carbon dioxide gas discharged through the second outlet 124 is supplied to the second inlet 122 through the carbon dioxide circulation supply unit 130.
  • the carbon dioxide circulation supply unit 130 recirculates the carbon dioxide gas discharged through the second outlet 224 to the second inlet 122 to re-supply it.
  • the connector 140 connects the first inlet port 112 of the first reaction space 111 and the communication port 123 of the receiving space 121.
  • the first reaction space 111 and the accommodation space 121 communicate with each other through a connection passage 141 formed inside the connection pipe 140.
  • Carbon dioxide gas that is not ionized because it is not dissolved in the first electrolyte 115 among the carbon dioxide introduced into the accommodation space 121 of the carbon dioxide processing unit 120 through the second inlet 122 is the first reaction space of the cathode 110
  • the carbon dioxide gas discharged through the second outlet 124 and discharged through the second outlet 124 after being collected in the space above the water surface of the first electrolyte 115 in the accommodation space 121 without being able to move to (111) Is supplied to the receiving space 121 through the second inlet 122 by the carbon dioxide circulation supply unit 130 is recycled.
  • carbon dioxide gas that is not ionized because it is not dissolved in the first electrolyte 115 among the carbon dioxide introduced into the accommodation space 121 of the carbon dioxide processing unit 120 does not move to the first reaction space 111 of the cathode 110. Since it is not possible, high-purity hydrogen in which carbon dioxide is not mixed may be discharged through the first outlet 113.
  • the secondary battery 300 includes a cathode unit 210, an anode unit 250, an electrolyte circulating unit 180 connected to the anode unit 250, a cathode unit 210, and an anode unit ( 250) includes a connecting portion 290 for connecting.
  • the cathode unit 210 includes a first reaction vessel 110a providing a first reaction space 111 therein, a first electrolyte solution 215 contained in the first reaction space 111, and a first electrolyte solution 215.
  • a first electrolyte solution 215. Is provided with a cathode (118) at least partially submerged.
  • an aqueous potassium hydroxide solution in this embodiment, an elution of CO 2 in a strong basic solution of 1M KOH is used
  • the configuration of the first reaction vessel 110a and the cathode 118 is the same as the corresponding configuration in the embodiment illustrated in FIG. 13, detailed description thereof will be omitted.
  • the anode unit 150 includes a second reaction container 150a providing a second reaction space 151 therein, a second electrolyte solution 155 contained in the second reaction space 151, and a second electrolyte solution 155 ) Is provided with an anode 158 in which at least a part is locked.
  • a second electrolyte solution 155 an aqueous potassium hydroxide solution is described, and for example, 1M KOH or 6M KOH may be used. Since the configuration of the second reaction vessel 150a and the anode 158 is the same as the corresponding configuration in the embodiment illustrated in FIG. 13, detailed description thereof will be omitted.
  • electrolyte circulating portion 180 is the same as the electrolyte circulating portion 180 illustrated in FIG. 13, detailed description thereof will be omitted.
  • connection part 290 includes a connection passage 191 connecting the cathode part 110 and the anode part 150, and an ion exchange membrane 192 installed inside the connection passage 191.
  • connection passage 191 has the same configuration as the connection passage 191 shown in FIG. 13, and an ion exchange membrane 192 is installed inside the connection passage 191.
  • the ion exchange membrane 192 is installed in a form that blocks the inside of the connection passage 191.
  • the ion exchange membrane 192 allows only the movement of ions between the cathode portion 110 and the anode portion 150.
  • the potassium ion (K + ) contained in the second electrolyte solution 155 is moved to the first electrolyte solution 115 by the ion exchange membrane 192.
  • a fluorine resin-based cation exchange membrane developed by DuPont, USA is used to describe that Nafion is used, but the present technology is not limited thereto, and potassium ion ( Anything that allows only the movement of K + ) is possible.
  • the ion exchange membrane 192 eliminates ion imbalance generated in the discharge process by transferring only ions.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, an electrolyte circulating unit 180 connected to the anode unit 150, a cathode unit 110, and an anode unit It includes a connecting portion 190 for connecting the 150, the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit 130, the cathode 110 and the connection pipe 140 for communicating the carbon dioxide processing unit 120.
  • the cathode unit 110, the anode unit 150, the electrolyte circulation unit 180, and the connection unit 190 are the same as described in the embodiment illustrated in FIG. 16, and the carbon dioxide processing unit 120 and the carbon dioxide circulation supply unit 130 And the connector 140 is the same as the corresponding configuration shown in Figure 15, a detailed description thereof will be omitted.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, an electrolyte circulation unit 180 connected to the anode unit 150, a cathode unit 110, and an anode unit It includes a connecting portion 190 for connecting the (150).
  • the cathode unit 110, the anode unit 150, and the electrolyte circulation unit 180 are the same as the corresponding configurations of the embodiment illustrated in FIG. 16, and thus detailed descriptions thereof will be omitted.
  • connection part 190 includes a connection passage 191 connecting the cathode part 110 and the anode part 150 and an ion exchange membrane 192 installed inside the connection passage 191.
  • connection passage 191 is the same as the connection passage 191 of the embodiment shown in FIG. 16, and an ion exchange membrane 192 is installed inside the connection passage 191.
  • the ion exchange membrane 192 is installed in a form that blocks the inside of the connection passage 191.
  • the ion exchange membrane 192 allows only the movement of ions between the cathode portion 110 and the anode portion 150.
  • the hydroxide ions contained in the first electrolyte solution (115) (OH -) is moved in the second electrolyte 155.
  • a fluorine resin-based cation exchange membrane Nafion developed by DuPont of the United States is used, but the present technology is not limited thereto, and hydroxide ions ( all as long as it is possible that only) movement of the - OH.
  • Hydroxide ions by an ion exchange membrane (192) (OH -) is written doemeu delivered from the cathode 110 to the anode 150, thereby eliminating the ion imbalance caused in the discharge process.
  • the secondary battery 100 includes a cathode unit 110, an anode unit 150, an electrolyte circulating unit 180 connected to the anode unit 150, a cathode unit 110, and an anode unit It includes a connecting portion 190 for connecting the 150, the carbon dioxide processing unit 120, the carbon dioxide circulation supply unit 130, the cathode 110 and the connection pipe 140 for communicating the carbon dioxide processing unit 120.
  • the cathode unit 110, the anode unit 150, the electrolyte circulation unit 180, and the connection unit 190 are the same as described in the embodiment illustrated in FIG. 18, and the carbon dioxide processing unit 120 and the carbon dioxide circulation supply unit 130 And the connector 140 is the same as the corresponding configuration shown in Figure 16, detailed description thereof will be omitted.
  • a salt bridge connecting the first electrolyte 115 and the second electrolyte 155 may be used instead of the connecting portion 190, which is also within the scope of the present technology. Belong.
  • a salt bridge an internal solution of a salt bridge that is commonly used, such as potassium chloride (KCl) or sodium chloride (NaCl), may be used as the internal solution of the salt bridge.
  • KCl potassium chloride
  • NaCl sodium chloride
  • HCO 3 ⁇ bicarbonate ions
  • sodium ions are diffused from the salt bridge and exist as ions in the form of an aqueous sodium hydrogen carbonate (NaHCO 3 ) solution.
  • NaHCO 3 aqueous sodium hydrogen carbonate
  • the metal recovery part 800 includes the same aqueous solution as the second electrolyte solution 155 of the anode part 150 or the aqueous solution 215 of the reaction space 211.
  • the metal recovery part 800 is a supply part 810 that receives the second electrolyte solution 155 used as the anode part 150 or the aqueous solution 215 used in the reaction space 211, and the supplied aqueous solution 155 or 215.
  • the supply unit 810 supplies an aqueous solution 155 or 215 in which metal ions are dissolved from the secondary battery 100 to the metal recovery unit 800.
  • the supply unit 810 may be selectively opened and closed at a suitable time by a valve or the like as necessary.
  • the second cathode 820 is at least partially submerged in the aqueous solution 155 or 215 accommodated in the recovery space 850, and is made of the same material as the anode 158.
  • the anode 158 of the secondary battery 100 is zinc (Zn)
  • Zn(OH) 4 2- is present in the supplied aqueous solution (155 or 215).
  • a reduction reaction such as the following [Reaction Scheme 9] may be performed.
  • the metal ions dissolved in the aqueous solution (155 or 215) supplied from the secondary battery 100 receive electrons from the second cathode 820 to become a metal. Can be reduced.
  • the second anode 830 is at least partially submerged in an aqueous solution accommodated in the recovery space 850, and is an electrode for forming an electrical circuit.
  • the material of the second anode 830 may be carbon paper, carbon fiber, carbon felt, carbon cloth, metal foam, metal thin film, or a combination thereof, and a platinum catalyst may also be used.
  • a platinum catalyst may also be used.
  • all other catalysts that can be generally used as an oxygen generating reaction (HER) catalyst such as a carbon-based catalyst, a carbon-metal-based composite catalyst, and a perovskite oxide catalyst, are also included.
  • the power supply unit 840 is electrically connected to the second cathode 820 and the second anode 830 to provide electricity.
  • the negative electrode of the power supply unit 840 is electrically connected to the second cathode 820 of the metal recovery unit 800, and the positive electrode of the power supply unit 840 is electrically connected to the second anode 830 of the metal recovery unit 800.
  • the power supply unit 840 is not limited thereto, and renewable energy such as solar cells and wind power generation may be used as well as general cells and generators.
  • the secondary battery of the present technology includes a cathode and a metal anode immersed in an electrolyte, which is an aqueous electrolyte, and the maximum current of the electrolyte in the secondary battery generating hydrogen gas by introducing carbon dioxide gas into the electrolyte during the discharge process is about twice the maximum current than room temperature.
  • the second electrolytic solution accommodated in the second reaction space is circulated by the electrolyte circulating portion, thereby slowing corrosion of the anode metal in the second reaction space, and washing the metal oxide which has been corroded and accumulated on the surface of the anode metal, thereby discharging capacity Can be greatly increased.
  • a metal recovery unit it is possible to recover the metal consumed in the secondary battery and remain in ionic form again with high purity.

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Abstract

Selon la présente technologie, l'invention concerne une batterie secondaire apte à charger et à décharger, comprenant : une unité de cathode comprenant un premier électrolyte qui est un électrolyte aqueux logé dans un premier espace de réaction, et une cathode qui est au moins partiellement immergée dans le premier électrolyte ; et une unité d'anode comprenant un second électrolyte qui est un électrolyte aqueux logé dans un second espace de réaction, et une anode qui est au moins partiellement immergée dans le second électrolyte, le dioxyde de carbone gazeux étant introduit dans le premier électrolyte, et des ions hydrogène et des ions bicarbonate étant générés par une réaction entre l'eau du premier électrolyte et le dioxyde de carbone gazeux, et les ions hydrogène et les électrons de la cathode étant combinés afin de générer de l'hydrogène gazeux.
PCT/KR2019/013460 2018-12-27 2019-10-15 Batterie secondaire générant de l'hydrogène à l'aide de dioxyde de carbone et système de génération d'énergie complexe doté de cette dernière WO2020138668A1 (fr)

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