WO2020175852A2 - 수소 생산을 위한 이차 전지 - Google Patents

수소 생산을 위한 이차 전지 Download PDF

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Publication number
WO2020175852A2
WO2020175852A2 PCT/KR2020/002494 KR2020002494W WO2020175852A2 WO 2020175852 A2 WO2020175852 A2 WO 2020175852A2 KR 2020002494 W KR2020002494 W KR 2020002494W WO 2020175852 A2 WO2020175852 A2 WO 2020175852A2
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WIPO (PCT)
Prior art keywords
anode
secondary battery
discharge
cathode
hydrogen
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Ceased
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PCT/KR2020/002494
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English (en)
French (fr)
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WO2020175852A3 (ko
Inventor
김영식
장지욱
황수민
한진협
이진호
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UNIST Academy Industry Research Corp
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UNIST Academy Industry Research Corp
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Publication of WO2020175852A2 publication Critical patent/WO2020175852A2/ko
Publication of WO2020175852A3 publication Critical patent/WO2020175852A3/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • H01M10/465—Accumulators structurally combined with charging apparatus with solar battery as charging system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a secondary battery, and more particularly, to a secondary battery for producing electricity and hydrogen at the same time through the charging and discharging process.
  • Hydrogen fuel is in the spotlight due to the development of clean new energy technology, and accordingly, it is being developed in various hydrogen storage systems.
  • Another hydrogen storage technology is the hydrogen movement and storage method using organic/inorganic chemical hydrides.
  • organic/inorganic chemical hydrides the reversibility of organic/inorganic chemical hydrides is considerably low, and the liquid organic hydrogen carrier is harmful to soil organic matter. May have a medicinal effect on the environment.
  • the present invention was created to solve the above-described problem, and its purpose is to provide a secondary battery for producing hydrogen at the same time as generating electricity through the charging and discharging process.
  • the present invention aims to provide a secondary battery capable of producing hydrogen at the same time as electricity generation by performing a discharge process with a high current discharge current.
  • this invention is an anode of the negative electrode, so a £ 32 anode is used to control the charging voltage.
  • the present invention one embodiment the leg which cathode unit comprising an anode (0 ⁇ ) is impregnated in an organic electrolyte according to; the cathode is impregnated in the containing sodium hydroxide solution (for ⁇ 0 ⁇ ); And a solid electrolyte that is positioned between the anode and the cathode to separate the anode and the cathode; and, by adjusting the discharge current, in the anode through a discharge reaction Hydrogen can be produced.
  • the magnitude of the discharge current may be 0.05111 show/0112 to 2 ⁇ /0112.
  • the anode part may include a distribution part through which hydrogen generated through the discharging process is discharged.
  • the anode portion may include an inlet portion for injecting an inert gas into the anode portion.
  • the sodium-containing solution may contain seawater & ⁇ burr.
  • the anode may include at least one of a sodium anode and a £ 32 anode.
  • the secondary battery may further include another anode portion including another cathode that is impregnated with a sodium-containing solution.
  • the cathode may be used in a discharge reaction of the secondary battery, and the other cathode may be used in a charging reaction of the secondary battery through a solar cell.
  • the anode part may include the cathode impregnated with a lithium-containing solution.
  • electrolyte Hydrogen can be produced at the same time as electricity production by conducting the discharge process with a high current discharge current, and by using seawater as a coolant, it is possible to control the high temperature generated during hydrogen production and minimize thermal risk.
  • FIG. 1 is a diagram showing a functional configuration of a secondary battery according to an embodiment of the present invention
  • [31] is a diagram showing a performance graph of a secondary battery when sea water is used as a positive electrode electrolyte according to an embodiment of the present invention.
  • Fig. 32 is a diagram showing a performance graph of a secondary battery when sodium sulfate is used as a positive electrode electrolyte according to an embodiment of the present invention.
  • FIG. 34 Figures and are diagrams showing Faraday efficiency and hydrogen production graphs for each cycle according to an embodiment of the present invention.
  • [35] is a diagram showing a charge/discharge voltage graph according to an embodiment of the present invention.
  • the diagram is a diagram showing a discharge voltage graph and a hydrogen generation rate graph according to an embodiment of the present invention.
  • FIG. 8 is a view showing a Faraday efficiency graph for a discharge current according to an embodiment of the present invention.
  • FIG. 9 is a view showing another functional configuration of a secondary battery according to an embodiment of the present invention.
  • Fig. 4 is a diagram showing a performance graph of a secondary battery when a £ 32 anode is used according to an embodiment of the present invention.
  • FIG. 1 is a diagram showing a functional configuration of a secondary battery 100 according to an embodiment of the present invention
  • the secondary battery 100 includes a positive electrode part 110, a negative electrode part 120, and a solid
  • Electrolyte 130 may be included.
  • the anode part 110 may include a cathode 110 (furnace) 112 impregnated with a sodium-containing solution and a water tank containing the sodium-containing solution.
  • the sodium-containing solution is the anode of the anode part (0). It is used as an electrolytic solution; for example, a sodium-containing solution may contain at least one of seawater and an aqueous solution of sodium sulfate (2304).
  • the anode part (0) contains sodium as the anode part (0) on one side
  • It may include a piping part 114 through which the solution is introduced or discharged.
  • the cathode 112 may comprise an anode current collector, which may be carbon felt, carbon paper, carbon fiber, metal thin film, or a combination thereof, and a catalyst layer provided on the anode current collector. That is, the cathode 112 ) May include a carbon cathode composed of a carbon material.
  • the cathode part 120 may include an anode (0 (no) 122) impregnated with an organic electrolyte (eg, TEGDME).
  • an organic electrolyte eg, TEGDME
  • the anode 122 is a sodium anode composed of sodium metal, lithium but it can include at least one of a moire £ anode 32 consisting of a lithium anode and a moire £ 32 consisting of a metal, the anode 122 may be a variety of materials and the material applied to the type of the anode 122 is not limited to this.
  • the anode electrolyte of the anode portion may be a lithium-containing aqueous solution.
  • the anode electrolyte of the anode portion may be a lithium-containing aqueous solution.
  • lithium-containing aqueous solution may be used.
  • the aqueous solution containing may include an aqueous solution of lithium sulfate.
  • the anode 122 is located on the cathode current collector and the cathode current collector.
  • an active material layer may be included.
  • the active material layer may be made of hard carbon (1131 (10 ⁇ 15011, ⁇ ), an organic material, or an alloy based material.
  • the positive electrode portion 110 to charge electrical energy
  • a reaction such as ⁇ Formula 2> to generate hydrogen while discharging electrical energy may occur in the anode part (no).
  • reactions such as the following ⁇ Chemical Formula 3> may occur in the cathode 120.
  • the ORR (oxygen reduction reaction) reaction was carried out by oxygen present on the cathode surface of the positive electrode, but referring to the above ⁇ Formula 5>, the secondary battery 100 according to an embodiment of the present invention
  • the discharge process takes place before oxygen is located on the surface of the cathode 112 of the positive electrode part (H0) by performing the discharge process at a high current, so that even though there is oxygen, oxygen cannot be used like an oxygen-free environment.
  • Hydrogen evolution reaction (HER) can proceed immediately. That is, in the case of the secondary battery W0 according to an embodiment of the present invention, by controlling the discharge current so that the hydrogen generation reaction occurs, the discharge reaction Through
  • Hydrogen can be produced at the anode portion (H0).
  • the high current can mean the discharge current, and the range of the discharge current in which the hydrogen generation reaction can occur can be 0.05mA/cm2 to 2mA/cm2.
  • the discharge current can mean the current density, and the solid state. It can represent the current generated relative to the cross-sectional area of the electrolyte 130. Therefore, even if the shape of the secondary battery 100 is various, such as a coin-type or a square pack-type, the same range for the hydrogen generation reaction A false discharge current can be applied.
  • the discharge capacity is accumulated while the hydrogen production amount can also be accumulated.
  • the amount of hydrogen produced through the discharge reaction can be expressed as a faradaic efficiency as shown in Equation 1 below.
  • the amount of hydrogen produced is generated. It can mean the molar concentration of hydrogen.
  • FE Faraday efficiency
  • n the number of electrons required for water reduction
  • F the Faraday constant (96485C/mol)
  • 3 ⁇ 4 is the molar concentration of hydrogen
  • I the discharge current
  • T the discharge time
  • hydrogen may be generated through the discharge process in the positive electrode portion 110 of the secondary battery 100 according to an embodiment of the present invention.
  • the positive electrode portion H0 is generated through the discharge process. It may include a discharge unit 116 from which the hydrogen is discharged.
  • the positive electrode portion (no) may include an inert gas (eg, argon gas (inlet portion 118) for injecting the shovel into the positive electrode portion (no).
  • an inert gas eg, argon gas (inlet portion 118) for injecting the shovel into the positive electrode portion (no).
  • a solid electrolyte 130 that passes sodium ions may be located.
  • the solid electrolyte may include NASICON or LISICON. .
  • FIGS. 2A and 2B are diagrams showing graphs of the amount of hydrogen produced when various types of anodes are used according to an embodiment of the present invention.
  • the secondary battery 100 uses seawater as the positive electrode electrolyte of the positive electrode part 110, and sodium metal as the anode 122 of the negative electrode part 120.
  • the configured sodium anode can be used. In this case, discharge
  • a secondary battery 100 uses a lithium sulfate aqueous solution as the positive electrolyte of the positive electrode part 110, and lithium as the anode 122 of the negative electrode part 120 A lithium anode composed of metal can be used.
  • the hydrogen production increases as the discharge capacity increases to l.OmAh.
  • the Faraday efficiency can be 90.2%.
  • the secondary battery 100 according to an embodiment of the present invention is
  • 3A is a view showing a performance graph of a secondary battery when seawater is used as a positive electrode electrolyte according to an embodiment of the present invention.
  • FIG. 3A a discharge voltage graph for a discharge current of 0.05mA/cm2,
  • the hydrogen production rate graph and the hydrogen production amount graph of the secondary battery 100 using seawater as the positive electrode electrolyte of the positive electrode part (H0) and sodium anode as the anode 122 of the negative electrode part 120 can be checked.
  • the flatness of the discharge voltage can be checked up to 0.5mAh of discharge capacity.
  • the amount of hydrogen produced increases as the discharge capacity increases up to 0.5 mAh. That is, the secondary battery 100 according to an embodiment of the present invention can discharge to 0.5 mAh capacity to generate electricity. At the same time, it can be seen that hydrogen production is also possible. At this time, the Faraday efficiency can be 99.7%.
  • 3B is a diagram showing a performance graph of a secondary battery when sodium sulfate is used as a positive electrode electrolyte according to an embodiment of the present invention.
  • FIG. 3B a discharge voltage graph for a discharge current of 0.05mA/cm2,
  • the hydrogen production rate graph and the hydrogen production amount graph of the secondary battery 100 using sodium sulfate as the anode electrolyte of the positive electrode part (H0) and sodium anode as the anode 122 of the negative electrode part 120 can be confirmed.
  • the flatness of the discharge voltage can be checked up to 0.5mAh of discharge capacity.
  • the amount of hydrogen produced increases as the discharge capacity increases up to 0.5 mAh. That is, the secondary battery 100 according to an embodiment of the present invention can discharge to 0.5 mAh capacity to generate electricity. At the same time, it can be seen that hydrogen production is also possible. At this time, the Faraday efficiency can be 91.8%.
  • Figures 4a and 4b are charge and discharge voltages for each cycle according to an embodiment of the present invention
  • a graph of the constant current charge/discharge voltage of the secondary battery 100 can be confirmed at a current of 0.5 mA/cm2 for 6 hours, respectively.
  • sea water oxidation oxygen generation and/
  • the charge and discharge voltage flatness can be confirmed as a result of seawater reduction (i.e. hydrogen generation) during the chloride oxidation reaction) and during the discharge process.
  • the secondary battery 100 is capable of metal water chemical reaction reversible H2 storage.
  • 5A and 5B are diagrams showing Faraday efficiency and hydrogen production graphs for each cycle according to an embodiment of the present invention.
  • the Faraday efficiency value is initially You can see what the gradual certification does, but you can see a constant Faraday efficiency value after being discharged for a certain period of time. In this case, a maximum Faraday efficiency of 82.6% can be achieved in periodic tests of each of these cycles.
  • the secondary battery 100 In the case of the hydrogen production amount, it is possible to confirm a constant hydrogen production amount according to the discharge time for each cycle. Through this, the secondary battery 100 according to an embodiment of the present invention has Faraday efficiency and hydrogen production amount even if the charge/discharge cycle proceeds. It can be confirmed that the performance is maintained.
  • FIG. 6A is a view showing a charge/discharge voltage graph according to an embodiment of the present invention.
  • FIG. 6B is a view showing a discharge voltage graph and a hydrogen generation rate graph according to an embodiment of the present invention.
  • the FeS2 electrode can check the reversible charge/discharge operation with a specific capacity of ⁇ 380mAh/g during subsequent cycles.
  • a FeS2 electrode is used as the anode 122 of the negative electrode 120, and has a capacity cut-off (250 mAh/g) and a voltage cut-off (0V) upon discharge.
  • a capacity cut-off 250 mAh/g
  • a voltage cut-off (0V) upon discharge.
  • the Faraday efficiency is lower than that of the sodium anode, but the result clearly shows that the microscale FeS2 electrode can be applied as the anode 122 of the negative electrode 120 of the secondary battery 100.
  • the operating voltage is reduced by IV or more compared to the case of using a sodium anode.
  • the performance of the secondary battery (W0) is excellent even in the air. That is, the maximum Faraday efficiency achieved during discharge at 0.05, 0.1, 0.5, 1.0, 1.5 and 2.0 mA/cm2, respectively, is approximately 8 , 28, 49, 64, 75, and 77%. Therefore, it can be seen that the Faraday efficiency increases at a high discharge current even in a natural environment. In this case, referring to FIG. 8, the Faraday efficiency increases as the discharge current increases. can confirm. 2020/175852 1»(:1 ⁇ 1 ⁇ 2020/002494
  • FIG 9 shows another functional configuration of a secondary battery 900 according to an embodiment of the present invention.
  • the secondary battery 900 includes a first positive electrode part 910, a negative electrode part 920, and a first solid
  • An electrolyte 930, a second positive electrode portion 940, and a second solid electrolyte 950 may be included.
  • the first anode part (this 0) may include a first cathode 912 impregnated with the sodium-containing solution and a water tank containing the sodium-containing solution.
  • the first anode part (this 0) In one side, the first positive electrode part 910 may include a pipe part 914 through which the sodium-containing solution is introduced or discharged.
  • the first cathode 912 may comprise a cathode current collector, which may be carbon felt, carbon paper, carbon fiber, metal thin film, or a combination thereof, and a catalyst layer provided on the anode current collector.
  • a cathode current collector which may be carbon felt, carbon paper, carbon fiber, metal thin film, or a combination thereof, and a catalyst layer provided on the anode current collector.
  • One cathode 912 may include a carbon cathode composed of a carbon material.
  • the first anode part 910 is for discharging the generated oxygen to the outside.
  • electrons generated in the first cathode 912 during charging may be transferred to the cathode part 920 through an external circuit electrically connected to the first cathode 912.
  • the first cathode 912 of the first anode portion 910 may be used in the charging reaction of the secondary battery 900.
  • the overall chemical formula of the secondary battery 900 may be expressed as shown in the following ⁇ Formula 6>.
  • the negative electrode part 920 may include an anode 922 impregnated with an organic electrolyte (eg, TEGDME).
  • the anode 922 may include a negative electrode current collector and an active material layer positioned on the negative electrode current collector.
  • the anode 922 can include at least one of a moire £ 32 anode consisting of lithium anode and moire £ 32 configured with a sodium anode, a lithium metal consisting of sodium metal, the anode 922 applies a variety of materials
  • the material type of the anode 922 is not limited thereto.
  • the charging voltage when a sodium anode is used as the anode 922, the charging voltage may be ⁇ 3.48 ⁇ . That is, the secondary battery 100 can be charged only when a high voltage of 3.48 ⁇ is applied during charging. However, when using a £ 32 anode compared to a sodium anode, the charging voltage may be lowered to ⁇ 2.4 ⁇ . In this case, as the charging voltage decreases, the secondary battery 900 can perform photovoltaic charging through the solar cell 960. It is possible to reduce the charging voltage or implement a self-charging system without external applied power, while simultaneously implementing a hydrogen generating system.
  • a reaction such as the following ⁇ Chemical Formula 7> 2020/175852 1»(:1/10 ⁇ 020/002494 May occur.
  • a first solid electrolyte 930 that moves from the anode portion 910 to the cathode portion 920 may be located.
  • This second positive electrode portion 940 may include a second cathode 942 impregnated with a sodium-containing solution and a water tank containing a sodium-containing solution.
  • the second positive electrode portion 940 is one side.
  • a pipe part 944 through which a sodium-containing solution is introduced or discharged into the second anode part 940 may be included.
  • the second cathode 942 may mean a cathode used in the second anode portion 940 when the secondary battery 900 is discharged.
  • the second cathode 942 during discharge is electrons from the cathode portion 920 That is, the second cathode 942 of the second anode 940 is
  • the second cathode 942 may comprise an anode current collector, which may be carbon felt, carbon paper, carbon fiber, metal thin film, or a combination thereof, and a catalyst layer provided on the anode current collector.
  • the two-cathode 942 may include a carbon cathode composed of a carbon material.
  • Hydrogen may be generated through a discharge process in the second anode part 940 of the secondary battery 900 according to an embodiment of the present invention.
  • the second anode part 940 performs a discharge process. It may include a discharge unit 946 through which hydrogen produced is discharged.
  • the second anode portion 940 may include an inlet portion 948 for injecting an inert gas (eg, argon gas) into the anode portion 920.
  • an inert gas eg, argon gas
  • oxygen existing in the hermetic structure inside the second anode part 940 can be removed.
  • [129] is a diagram showing a performance graph of a secondary battery when a £ 32 anode is used according to an embodiment of the present invention.
  • the flat portion of the discharge voltage can be checked until the discharge capacity is 250 111 Show 11.
  • the amount of hydrogen produced increases as the discharge capacity increases until the discharge capacity is 250 ⁇ 11 show 11. That is, the secondary battery according to an embodiment of the present invention can generate electricity by discharging to 250 111 show 11 capacity, At the same time, it can be confirmed that hydrogen production is also possible, at this time, the Faraday efficiency can be 74.9%.

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  • Electrochemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

본 발명은 충방전 과정을 통해 전기를 생산함과 동시에 수소를 생산하기 위한 이차 전지에 관한 것이다. 본 발명의 일 실시예에 따른 이차전지는 유기 전해질에 함침되는 애노드(anode)를 포함하는 음극부; 나트륨 함유 용액에 함침되는 캐소드(cathode)를 포함하는 양극부; 및 상기 양극부와 상기 음극부 사이에 위치하여 상기 양극부와 상기 음극부를 분리하는 고체 전해질;을 포함하고, 방전 전류를 조절함에 따라, 방전 반응을 통해 상기 양극부에서 수소가 생성될 수 있다.

Description

2020/175852 1»（：1/10公020/002494 명세서
발명의명칭:수소생산을위한이차전지 기술분야
[I] 본발명은이차전지에관한것으로,더욱상세하게는충방전과정을통해 전기를생산함과동시에수소를생산하기위한이차전지에관한것이다.
四
배경기술
[3] 청정신에너지기술개발로수소연료가각광받고있으며 ,이에따라여러가지 수소저장시스템에개발되고있다.
[4] 수소저장기술중하나는금속또는그화합물이수소와반응하여금속
수소화물을형성하는고체상태의저장방식이다.그러나,이러한금속 수소화물은상대적으로낮은중량수소밀도,제한된탈수소화속도,낮은 가역효율및수소방출에필요한고온으로인해효과적인수소저장시스템으로 간주될수없다.
[5] 또다른수소저장기술중하나는유기/무기화학수소화물을이용한수소 운동및저장방식이다.다만,유기/무기화학수소화물의가역성은상당히 낮으며 ,액체유기수소운반체는토양유기물에유해하므로환경에약영향을 미칠수있다.
[6] 또한,수소생성기술로알칼리금속과물의화학반응을이용하는방식이 있으나,이는비가역성의문제가있다.여기서,비가역성은수소생산을위해 알칼리금속을재사용할수없음을의미한다.또한,알칼리금속기반의수소 생성기술은의경우,알칼리금속이대기및습기와접촉할대쉽게금속산화물 및수산화물을형성하여보관및사용에특별한시설및보호가필요로하는 문제점이 있다.
[7]
발명의상세한설명
기술적과제
[8] 본발명은전술한문제점을해결하기위하여창출된것으로,충방전과정을 통해전기를생산함과동시에수소를생산하기위한이차전지를제공하는것을 그목적으로한다.
[9] 또한,본발명은고전류의방전전류로방전과정을진행함으로써,전기생산과 동시에수소를생산할수있는이차전지를제공하는것을그목적으로한다.
[1이 또한,본발명은음극부의애노드로므£32애노드를사용하여충전전압을
낮춤으로써,태양광충전을통한자가충전시스템을구현하는이차전지를 제공하는것을그목적으로한다.
[I I] 본발명의목적들은이상에서언급한목적들로제한되지않으며,언급되지 2020/175852 1»（：1^1{2020/002494 않은또다른목적들은아래의 기재로부터 명확하게 이해될수있을것이다.
[12]
과제해결수단
[13] 상기한목적들을달성하기위하여,본발명의 일실시예에따른이차전지는 유기 전해질에함침되는애노드（ 0此）를포함하는음극부;나트륨함유용액에 함침되는캐소드（대出0此）를포함하는양극부;및상기 양극부와상기 음극부 사이에 위치하여상기 양극부와상기 음극부를분리하는고체전해질;을 포함하고,방전전류를조절함에 따라,방전반응을통해상기 양극부에서 수소가생성될수있다.
[14] 실시예에서 ,상기방전전류의크기는, 0.05111쇼/0112내지 2^/0112일수있다.
[15] 실시예에서,상기 양극부는,상기 방전과정을통해생성된수소가배출되는 배줄부;를포함할수있다.
[16] 실시예에서,상기 양극부는,상기 양극부내부에불활성기체를주입하기위한 유입부;를포함할수있다.
[17] 실시예에서,상기나트륨함유용액은,해수 &\¥ 버를포함할수있다.
[18] 실시예에서 ,상기 애노드는,나트륨애노드및므£32애노드중적어도하나를 포함할수있다.
[19] 실시예에서,상기 이차전지는나트륨함유용액에함침되는다른캐소드를 포함하는다른양극부;를더포함할수있다.
[2이 실시예에서 ,상기 캐소드는,상기 이차전지의방전반응에서사용되고,상기 다른캐소드는,태양전지를통한상기 이차전지의충전반응에서사용될수 있다.
[21] 실시예에서，상기 양극부는,리튬함유용액에 함침되는상기 캐소드를포함할 수있다.
[22]
[23] 상기한목적들을달성하기위한구체적인사항들은첨부된도면과함께
상세하게후술될실시예들을참조하면명확해질것이다.
[24] 그러나,본발명은이하에서 개시되는실시예들에 한정되는것이아니라,서로 다른다양한형태로구성될수있으며 ,본발명의 개시가완전하도록하고본 발명이속하는기술분야에서통상의지식을가진자（이하, "통상의
기술자”）에게발명의범주를완전하게알려주기 위해서제공되는것이다.
[25]
발명의효과
[26] 본발명의 일실시예에 의하면,양극전해액으로
Figure imgf000004_0001
용하고 고전류의 방전전류로방전과정을진행함으로써,전기 생산과동시에수소를 생산할수있고,해수를냉각제로사용하여수소생산시 발생하는고온을 제어하고열적위험을최소화할수있다. 2020/175852 1»（：1^1{2020/002494
[27] 본발명의효과들은상술된효과들로제한되지않으며，본발명의기술적
특징들에의하여기대되는잠정적인효과들은아래의기재로부터명확하게 이해될수있을것이다.
[28]
도면의간단한설명
[29] 도 1은본발명의일실시예에따른이차전지의기능적구성을도시한
도면이다.
[3이
Figure imgf000005_0001
다양한종류의애노드를사용한
경우의수소생성량그래프를도시한도면이다.
[31] 도 는본발명의일실시예에따른양극전해액으로해수를사용한경우의 이차전지의성능그래프를도시한도면이다.
[32] 도 는본발명의일실시예에따른양극전해액으로황산나트륨을사용한 경우의이차전지의성능그래프를도시한도면이다.
[33]
Figure imgf000005_0002
충방전전압
그래프를도시한도면이다.
[34] 도 및 는본발명의일실시예에따른각사이클에대한패러데이효율및 수소생성량그래프를도시한도면이다.
[35] 도 는본발명의일실시예에따른충방전전압그래프를도시한도면이다.
[36] 도해는본발명의일실시예에따른방전전압그래프및수소생성율그래프를 도시한도면이다.
[37] 도 %및개는본발명의일실시예에따른다양한방전전류에대한충방전
전압그래프및수소생산성능그래프를도시한도면이다.
[38] 도 8은본발명의일실시예에따른방전전류에대한패러데이효율그래프를 도시한도면이다.
[39] 도 9는본발명의일실시예에따른이차전지의다른기능적구성을도시한 도면이다.
[4이 도 은본발명의일실시예에따른므£32애노드를사용한경우의이차전지의 성능그래프를도시한도면이다.
[41]
발명의실시를위한최선의형태
[42] 본발명은다양한변경을가할수있고,여러가지실시예들을가질수있는바, 특정실시예들을도면에 예시하고이를상세히설명하고자한다.
[43] 청구범위에개시된발명의다양한특징들은도면및상세한설명을고려하여 더잘이해될수있을것이다.명세서에개시된장치 ,방법，제법및다양한 실시예들은예시를위해서제공되는것이다.개시된구조및기능상의특징들은 통상의기술자로하여금다양한실시예들을구체적으로실시할수있도록하기 위한것이고,발명의범위를제한하기위한것이아니다.개시된용어및 2020/175852 1»（：1^1{2020/002494 문장들은개시된발명의다양한특징들을이해하기 쉽게설명하기위한것이고, 발명의 범위를제한하기 위한것이 아니다.
[44] 본발명을설명함에 있어서,관련된공지기술에 대한구체적인설명이본
발명의요지를불필요하게흐릴수있다고판단되는경우,그상세한설명을 생략한다.
[45] 이하,본발명의 일실시예에 따른충방전과정을통해 전기를생산함과동시에 수소를생산하기위한이차전지를설명한다.
[46]
[47] 도 1은본발명의 일실시예에 따른이차전지 (100)의기능적구성을도시한
도면이다.
[48] 도 1을참고하면,이차전지 (100)는양극부 (110),음극부 (120)및고체
전해질 (130)을포함할수있다.
[49] 양극부 (110)는나트륨함유용액에함침되는캐소드仁 110(노)(112)와나트륨 함유용액이담기는수조를포함할수있다.여기서,나트륨함유용액은 양극부 ( 0)의 양극전해액으로이용된다.예를들어,나트륨함유용액은 해수 및황산나트륨 ( 2304)수용액중적어도하나를포함할수있다.
[5이 일실시예에서,양극부 ( 0)는일측면에 양극부 ( 0)내부로나트륨함유
용액이유입되거나배출되는배관부 (114)를포함할수있다.
[51] 예를들어,캐소드 (112)는카본펠트,카본페이퍼,카본파이버,금속박막또는 이들의조합일수있는양극집전체및 양극집전체상에마련된촉매층을 포함할수있다.즉,캐소드 (112)는카본소재로구성된카본캐소드를포함할수 있다.
[52] 음극부 (120)는유기 전해질 (예 : TEGDME)에함침되는애노드 ( 0(노)(122)를 포함할수있다.예를들어,애노드 (122)는나트륨금속으로구성된나트륨 애노드,리튬금속으로구성된리튬애노드및므£32로구성된므£32애노드중 적어도하나를포함할수있으나,애노드 (122)는다양한소재가적용될수있으며 애노드 (122)의소재종류는이에 제한되지 않는다.
[53] 일실시예에서,음극부 (120)의 애노드 (122)가리튬금속으로구성되는경우, 양극부 (:나0)의 양극전해액은리튬함유수용액이사용될수있다.예를들어, 리튬함유수용액은황산리튬 (02304)수용액을포함할수있다.
[54] 일실시예에서 ,애노드 ( 122)는음극집전체및음극집전체상에위치하는
활물질층을포함할수있다.일실시예에서,활물질층은하드카본 (1131(1 0^15011, ^),유기물계 재료,또는합금계 재료로구성될수있다.
[55] 일실시예에서，충전시,양극부 (110)에서는전기 에너지를충전하는하기
＜화학식 1＞과같은반응이 발생할수있다.
[56] [화학식 1]
40H~ (aq) ® 02 + 2/#20 + 461
Figure imgf000006_0001
[57] 일실시예에서,방전시,양극부 (no)에서는전기에너지를방전하면서수소를 발생시키는하기＜화학식 2＞와같은반응이발생할수있다.
[58] [화학식 2]
Figure imgf000007_0001
[59] 일실시예에서 ,충방전시 ,음극부 (120)에서는하기＜화학식 3＞과같은반응이 발생할수있다.
[6이 [화학식 3]
Charge
Na+ + e- 7 _{s); r = -2J1V vs.NHE
Discharge
[61] 즉,충전시,이차전지 (WO)의전체화학식은하기＜화학식 4＞와같이표현될수 있다.
[62] [화학식 4]
4Na(s) + 2H20(l) + DO{aq) ® 4NaOH(aq); £ 广 3.48F vs.Na*/Na mpH 8
[63]
[64] 또한,방전시,이차전지 (100)의전체화학식은하기＜화학식 5＞와같이표현될 수있다.
[65] [화학식 5]
2Na(s) + 2#¾0(1) ® H2(g) + 2Na* + OH (aq); Em„ = 2.241 vs. NHE at pH 8
[66] 이때,종래의경우양극부의캐소드표면에존재하는산소에의해 ORR(oxygen reduction reaction)반응이진행되었으나,상기＜화학식 5＞를참고하면,본발명의 일실시예에따른이차전지 (100)의경우,고전류로방전과정을진행함으로써, 산소가양극부 (H0)의캐소드 (112)표면에위치하기도전에방전과정이 일어남에따라산소가있음에도불구하고산소가없는환경처럼산소를 이용하지못하고바로수소생성반응 (HER(hydrogen evolution reaction))이 진행될수있다.즉,본발명의일실시예에따른이차전지 (W0)의경우,수소생성 반응이일어나도록방전전류를조절함에따라,방전반응을통해
양극부 (H0)에서수소가생성될수있다.
[67] 이경우,고전류는방전전류를의미할수있으며,수소생성반응이일어날수 있는방전전류의범위는 0.05mA/cm2내지 2mA/cm2일수있다.여기서,방전 전류는전류밀도를의미할수있으며,고체전해질 (130)의단면적대비발생되는 전류를나타낼수있다.따라서,이차전지 (100)의형태가코인형 (coin-type),사각 팩형 (pack-type)등다양하더라도수소생성반응을위하여동일한범위의방전 전류가적용될수있다.
[68] 일실시예에서,방전전류가설정되었을때,방전용량이누적되면서동시에 수소생산량또한누적될수있다. [69]
P이 일실시예에서 ,방전전류를조절함에따라,방전반응을통해생성되는수소 생성량은하기＜수학식 1＞과같이패러데이효율 (faradaic efficiency)로표현될수 있다.예를들어,수소생성량은생성된수소의몰농도를의미할수있다.
m] [수식 1]
FE = nF[H£ /IT
[72] 여기서 , FE는패러데이효율, n은물환원 (water reduction)에필요한전자의수, F는패러데이상수 (96485C/mol), ¾는수소의몰농도, I는방전전류, T는방전 시간을의미할수있다.
3] 따라서，본발명의일실시예에따른이차전지 (100)의양극부 (110)에서는방전 과정을통해수소가발생될수있다.일실시예에서,양극부 (H0)는방전과정을 통해생성된수소가배출되는배출부 (116)를포함할수있다.
4] 일실시예에서,양극부 (no)는양극부 (no)내부에불활성기체 (예:아르곤 가스 (쇼대를주입하기위한유입부 (118)를포함할수있다.이경우,불활성 기체를주입함으로써,양극부 (H0)내부의밀폐구조안에존재하는산소를 제거할수있다.
5] 양극부 (110)와음극부 (120)사이에는,양극부 (110)와음극부 (120)를
분리하면서,이차전지 (100)의충방전반응에서,나트륨이온을통과시키는고체 전해질 (130)이위치할수있다.예를들어,고체전해질은나시콘 (NASICON) 또는리시콘 (LISICON)을포함할수있다.
P6]
7] 도 2a및 2b는본발명의일실시예에따른다양한종류의애노드를사용한 경우의수소생성량그래프를도시한도면이다.
8] 도 2a를참고하면,본발명의일실시예에따른이차전지 (100)는양극부 (110)의 양극전해액으로해수를사용하고,음극부 (120)의애노드 (122)로나트륨 금속으로구성된나트륨애노드를사용할수있다.이경우,방전
용량 (capacity)이 l.OmAh까지는증가할수록수소생성량이증가함을확인할수 있다.이때,패러데이효율은 95.0%일수있다.
9] 도 2b를참고하면,본발명의일실시예에다른이차전지 (100)는양극부 (110)의 양극전해액으로황산리튬수용액을사용하고,음극부 (120)의애노드 (122)로 리튬금속으로구성된리튬애노드를사용할수있다.이경우또한,방전용량이 l.OmAh까지는증가할수록수소생성량이증가함을확인할수있다.이때, 패러데이효율은 90.2%일수있다.
[8이 즉,도 2a및 2b를참고하면,본발명의일실시예에따른이차전지 (100)는
l.OmAh용량까지방전하여전기를생산할수있고,동시에수소생산도 가능함을확인할수있다. [82] 도 3a는본발명의일실시예에따른양극전해액으로해수를사용한경우의 이차전지의성능그래프를도시한도면이다.
[83] 도 3a를참고하면, 0.05mA/cm2의방전전류에대한방전전압그래프,
양극부 (H0)의양극전해액으로해수를사용하고,음극부 (120)의애노드 (122)로 나트륨애노드를사용한이차전지 (100)의수소생성율그래프및수소생성량 그래프를확인할수있다.
[84] 이경우,방전용량이 0.5mAh까지는방전전압의평탄부를확인할수있다. 또한,방전용량이 0.5mAh까지는방전용량이증가할수록수소생성량이 증가함을확인할수있다.즉,본발명의일실시예에따른이차전지 (100)는 0.5mAh용량까지방전하여전기를생산할수있고,동시에수소생산도 가능함을확인할수있다.이때,패러데이효율은 99.7%일수있다.
[85]
[86] 도 3b는본발명의일실시예에따른양극전해액으로황산나트륨을사용한 경우의이차전지의성능그래프를도시한도면이다.
[87] 도 3b를참고하면, 0.05mA/cm2의방전전류에대한방전전압그래프,
양극부 (H0)의양극전해액으로황산나트륨을사용하고,음극부 (120)의 애노드 (122)로나트륨애노드를사용한이차전지 (100)의수소생성율그래프및 수소생성량그래프를확인할수있다.
[88] 이경우,방전용량이 0.5mAh까지는방전전압의평탄부를확인할수있다. 또한,방전용량이 0.5mAh까지는방전용량이증가할수록수소생성량이 증가함을확인할수있다.즉,본발명의일실시예에따른이차전지 (100)는 0.5mAh용량까지방전하여전기를생산할수있고,동시에수소생산도 가능함을확인할수있다.이때,패러데이효율은 91.8%일수있다.
[89]
[9이 도 4a및 4b는본발명의일실시예에따른각사이클에대한충방전전압
그래프를도시한도면이다.
[91] 도 4a를참고하면,각각 6시간동안 0.5mA/cm2의전류에서이차전지 (100)의 정전류충방전전압그래프를확인할수있다.각사이클에서,충전과정동안 해수산화 (산소발생및/또는염화물산화반응)및방전과정동안해수환원 (즉, 수소발생)결과로충전및방전전압평탄부를확인할수있다.
[92] 도 4b를참고하면, 70시간동안안정적인충방전전압그래프를확인할수
있으며,이를통해,본발명의일실시예에따른이차전지 (100)는금속수화학 반응가역 H2저장 (metal water chemical reaction reversible H2 storage)이가능함을 확인할수있다.
[93]
[94] 도 5a및 5b는본발명의일실시예에따른각사이클에대한패러데이효율및 수소생성량그래프를도시한도면이다.
[95] 도 5a및 5b를참고하면,각사이클에대하여 ,패러데이효율값은초기에 점진적인증가하는것을확인할수있지만,일정시간방전된후패러데이효율 값의일정한것을확인할수있다.이경우,이러한각사이클의주기적시험에서, 82.6%의최대패러데이효율이달성될수있다.
[96] 수소생성량의경우,각사이클마다방전시간에따른일정한수소생산량을 확인할수있다.이를통해,본발명의일실시예에따른이차전지 (100)는충방전 사이클이진행되더라도패러데이효율및수소생성량성능이유지됨을확인할 수있다.
[97]
[98] 도 6a는본발명의일실시예에따른충방전전압그래프를도시한도면이다.도 6b는본발명의일실시예에따른방전전압그래프및수소생성율그래프를 도시한도면이다.
[99] 도 6a를참고하면, 20mA/g의전류레이트 (current rate)에서 ,음극부 (120)의
애노드 (122)로 FeS2전극을사용한이차전지 (100) (예:하프-셀)의정전류충방전 전압그래프를확인할수있다.즉,표면상에고체전해질중간계 (interphase) 형성으로인한최초의비가역사이클링이후 (쿨롱효율〜 75%), FeS2전극은후속 사이클동안 ~380mAh/g의특정용량을갖는가역적인충방전동작을확인할수 있다.
[100] 도 6b를참고하면,음극부 (120)의애노드 (122)로 FeS2전극을사용하고,충전시 용량컷 -오프 (250 mAh/g)및방전시전압컷 -오프 (0V)를갖는 0.1 mA/cm2의 전류밀도에서사이클링을수행하는경우, 83.9%의패러데이효율과함께 대량의 H2생성을확인할수있다.
[101] 이경우,패러데이효율은나트륨애노드의효율보다낮지만,결과는분명히 마이크로스케일의 FeS2전극을이차전지 (100)의음극부 (120)의애노드 (122)로 적용가능하다는것을확인할수있다.또한,이경우,나트륨애노드를사용하는 경우에비해동작전압이 IV이상감소함을알수있다.
[102]
[103] 도 7a및개는본발명의일실시예에따른다양한방전전류에대한충방전
전압그래프및수소생산성능그래프를도시한도면이다.
[104] 도 7a및 7f를참고하면,자연환경 (natural environment)에서 ,즉, Ar가스로
이차전지 (100)를퍼징 (purge)시키지않고이차전지 (100)의성능을확인하기 위해, 6시간동안 0.05, 0.1, 0.5, 1.0, 1.5및 2.0 mA/cm2의방전전류로실험을 수행하였다.
[105] 이경우,대기중에서도이차전지 (W0)의성능이우수함을확인할수있다.즉, 0.05, 0.1, 0.5, 1.0, 1.5및 2.0mA/cm2각각에서방전하는동안달성된최대 패러데이효율은각각약 8, 28, 49, 64, 75및 77%였다.따라서 ,자연환경에서도 패러데이효율은높은방전전류에서높아짐을확인할수있다.이경우,도 8을 참고하면,방전전류가높아짐에따라패러데이효율이증가함을확인할수 있다. 2020/175852 1»（：1^1{2020/002494
[106]
[107] 도 9는본발명의일실시예에따른이차전지 (900)의다른기능적구성을
도시한도면이다.
[108] 도 9를참고하면,이차전지 (900)는제 1양극부 (910),음극부 (920),제 1고체
전해질 (930),제 2양극부 (940)및제 2고체전해질 (950)을포함할수있다.
[109] 제 1양극부 (이 0)는나트륨함유용액에함침되는제 1캐소드 (912)및나트륨 함유용액이담기는수조를포함할수있다.일실시예에서,제 1양극부 (이 0)는일 측면에제 1양극부 (910)내부로나트륨함유용액이유입되거나배출되는 배관부 (914)를포함할수있다.
[110] 예를들어,제 1캐소드 (912)는카본펠트,카본페이퍼,카본파이버,금속박막 또는이들의조합일수있는양극집전체및양극집전체상에마련된촉매층을 포함할수있다.즉,제 1캐소드 (912)는카본소재로구성된카본캐소드를포함할 수있다.
[111] 일실시예에서,제 1양극부 (910)는발생된산소를외부로배출하기위한
배출부 (916)를포함할수있다.또한,충전시제 1캐소드 (912)에서발생된전자는 제 1캐소드 (912)와전기적으로연결된외부회로를통해음극부 (920)로전달될 수있다.즉,제 1양극부 (910)의제 1캐소드 (912)는이차전지 (900)의충전 반응에서사용될수있다.
[112] 일실시예에서,충전시,이차전지 (900)의전체화학식은하기＜화학식 6＞과 같이표현될수있다.
[113] [화학식 6]
Figure imgf000011_0001
[114]
[115] 음극부 (920)는유기전해질 (예: TEGDME)에함침되는애노드 (922)를포함할수 있다.애노드 (922)는음극집전체및음극집전체상에위치하는활물질층을 포함할수있다.예를들어,애노드 (922)는나트륨금속으로구성된나트륨 애노드,리튬금속으로구성된리튬애노드및므£32로구성된므£32애노드중 적어도하나를포함할수있으나,애노드 (922)는다양한소재가적용될수있으며 애노드 (922)의소재종류는이에제한되지않는다.
[116] 일실시예에서,애노드 (922)로나트륨애노드를사용하는경우충전전압이 ~3.48¥일수있다.즉,충전시 3.48\^의높은전압을가해야만이차전지 (100)의 충전이가능하다.하지만,나트륨애노드대비므£32애노드를사용하는경우, 충전전압이 ~2.4¥로낮아질수있으며,이경우,충전전압이낮아짐에따라 이차전지 (900)는태양전지 (960)를통한광충전을수행할수있어충전전압을 낮추거나외부인가전원없이자가충전시스템을구현하면서,동시에수소 생성시스템을구현할수있다.
[117] 일실시예에서 ,충방전시음극부 (920)에서는하기＜화학식 7＞과같은반응이 2020/175852 1»（：1/10公020/002494 발생할수있다.
[118] [화학식7]
Figure imgf000012_0001
[119] 제 1양극부 (910)와음극부 (920)사이에는,제 1양극부 (910)와음극부 (920)를 분리하면서,이차전지 (900)의충전반응시,나트륨이온어버을통과시켜제 1 양극부 (910)로부터음극부 (920)로이동시키는제 1고체전해질 (930)이위치할수 있다.
[12이 제 2양극부 (940)는나트륨함유용액에함침되는제 2캐소드 (942)및나트륨 함유용액이담기는수조를포함할수있다.일실시예에서,제 2양극부 (940)는일 측면에제 2양극부 (940)내부로나트륨함유용액이유입되거나배출되는 배관부 (944)를포함할수있다.
[121] 제 2캐소드 (942)는이차전지 (900)의방전시제 2양극부 (940)에서이용되는 캐소드를의미할수있다.이경우,방전시제 2캐소드 (942)는음극부 (920)로부터 전자를전달받을수있다.즉,제 2양극부 (940)의제 2캐소드 (942)는
이차전지 (900)의방전반응에서사용될수있다.
[122] 예를들어,제 2캐소드 (942)는카본펠트,카본페이퍼,카본파이버 ,금속박막 또는이들의조합일수있는양극집전체및양극집전체상에마련된촉매층을 포함할수있다.즉,제 2캐소드 (942)는카본소재로구성된카본캐소드를포함할 수있다.
[123] 또한,방전시,이차전지 (900)의전체화학식은하기＜화학식 8＞과같이표현될 수있다.
[124] [화학식 8]
2· (多) + 2^0(0 ® ■2 (、0') + 2 . + ◎■，｛後 4)
[125] 본발명의일실시예에따른이차전지 (900)의제 2양극부 (940)에서는방전 과정을통해수소가발생될수있다.일실시예에서,제 2양극부 (940)는방전 과정을통해생성된수소가배출되는배출부 (946)를포함할수있다.
[126] 일실시예에서,제 2양극부 (940)는양극부 (920)내부에불활성기체 (예:아르곤 가스 ]·))를주입하기위한유입부 (948)를포함할수있다.이경우,불활성 기체를주입함으로써,제 2양극부 (940)내부의밀폐구조안에존재하는산소를 제거할수있다.
[127] 제 2양극부 (940)와음극부 (920)사이에는,제 2양극부 (940)와음극부 (920)를 분리하면서,이차전지 (900)의방전반응시,나트륨이온어버을통과시켜 음극부 (920)로부터제 2양극부 (940)로이동시키는제 2고체전해질 (950)이 위치할수있다. 2020/175852 1»（：1^1{2020/002494
[129] 도 은본발명의 일실시예에 따른므£32애노드를사용한경우의 이차전지의 성능그래프를도시한도면이다.
[13이 도 을참고하면, 0.05111쇼/0112의 방전전류에 대한방전전압그래프,
양극부 ( 0)의 양극전해액으로해수를사용하고,음극부 (120)의 애노드 (122)로 므 32애노드를사용한이차전지의수소생성율그래프및수소생성량그래프를 확인할수있다.
[131] 이경우,방전용량이 250111쇼11 까지는방전전압의 평탄부를확인할수있다. 또한,방전용량이 250å11쇼11 까지는방전용량이증가할수록수소생성량이 증가함을확인할수있다.즉,본발명의 일실시예에 따른이차전지는 250111쇼11 용량까지 방전하여 전기를생산할수있고,동시에수소생산도가능함을확인할 수있다.이 때,패러데이 효율은 74.9%일수있다.
[132]
[133] 이상의설명은본발명의 기술적사상을예시적으로설명한것에불과한
것으로,통상의 기술자라면본발명의본질적인특성이벗어나지 않는범위에서 다양한변경 및수정이가능할것이다.
[134] 따라서,본명세서에 개시된실시예들은본발명의 기술적사상을한정하기 위한것이아니라,설명하기 위한것이고,이러한실시예들에의하여본발명의 범위가한정되는것은아니다.
[135] 본발명의보호범위는청구범위에 의하여해석되어야하며,그와동등한범위 내에 있는모든기술사상은본발명의 권리범위에포함되는것으로이해되어야 한다.

Claims

2020/175852 1»（：1/10公020/002494 청구범위
[청구항 1] 유기전해질에함침되는애노드（ 0此）를포함하는음극부;
나트륨함유용액에함침되는캐소드 此）를포함하는양극부;및 상기양극부와상기음극부사이에위치하여상기양극부와상기 음극부를분리하는고체전해질;
을포함하고,
방전전류를조절함에따라,방전반응을통해상기양극부에서수소가 생성되는,
이차전지.
[청구항 2] 제 1항에 있어서,
상기방전전류의크기는, 0.0511^/ 112내지 2!11쇼/ 112인, 이차전지.
[청구항 3] 제 1항에 있어서,
상기양극부는,상기방전과정을통해생성된수소가배출되는배출부; 를포함하는,
이차전지.
[청구항 4] 제 1항에 있어서,
상기양극부는,상기양극부내부에불활성기체를주입하기위한유입부; 를포함하는,
이차전지.
[청구항 5] 제 1항에 있어서,
상기나트륨함유용액은,해수（86&\¥ ）를포함하는,
이차전지.
[청구항 6] 제 1항에 있어서,
상기애노드는,나트륨애노드및므632애노드중적어도하나를
포함하는,
이차전지.
[청구항 7] 제 1항에 있어서,
나트륨함유용액에함침되는다른캐소드를포함하는다른양극부;
를더포함하는,
이차전지.
[청구항 8] 제 7항에 있어서,
상기캐소드는,상기이차전지의방전반응에서사용되고, 상기다른캐소드는,태양전지를통한상기이차전지의충전반응에서 사용되는,
이차전지.
[청구항 9] 제 1항에 있어서, 2020/175852 1»（：1/10公020/002494 상기양극부는,리튬함유용액에함침되는상기캐소드를포함하는, 이차전지.
PCT/KR2020/002494 2019-02-27 2020-02-20 수소 생산을 위한 이차 전지 Ceased WO2020175852A2 (ko)

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