KR101955693B1 - Aqueous secondary battery using carbon dioxide and complex battery system having the same - Google Patents

Abstract

According to the present invention, provided is an aqueous secondary battery comprising a cathode part having an aqueous electrolyte contained in a first accommodation space and a cathode impregnated in the aqueous electrolyte; an anode part having an organic electrolyte contained in a second accommodation space and an anode impregnated in the organic electrolyte and including sodium metal; and a solid electrolyte arranged so as to selectively pass sodium ions between the cathode part and the anode part. The aqueous secondary battery, in which a reaction as shown in the following reaction formula 4, 2Na(s) + 2CO_2(aq) + 2H_2O(l) → 2NaHCO_3(aq) + H_2(g), is carried out by carbon dioxide supplied from the outside at the time of discharging.

Description

TECHNICAL FIELD [0001] The present invention relates to a water-based secondary battery using carbon dioxide, and a composite battery system using the same. BACKGROUND ART [0002]

The present invention relates to a water-based secondary battery, and more particularly, to a water-based secondary battery using carbon dioxide, which is a greenhouse gas, and a composite battery system having the water-based secondary battery.

In recent years, greenhouse gas emissions have been continuously increasing along with industrialization, and carbon dioxide is the largest proportion of greenhouse gases. CO2 emissions by industry type are highest in energy supply sources such as power plants, and carbon dioxide generated in cement / steel / refining industries including power generation accounts for about half of the global generation. The carbon dioxide conversion / utilization fields can be classified into chemical conversion, biological conversion, and direct utilization. The technical categories can be classified into catalyst, electrochemical, bioprocess, light utilization, inorganic (carbonation), and polymer. Because carbon dioxide is generated in a variety of industries and processes, and one technique can not achieve carbon dioxide reduction, a variety of approaches are needed to reduce carbon dioxide.

Currently, Department of Energy (DOE) of the US Department of Energy is pursuing multi-technology development with interest in CCUS technology, which is a combination of Carbon Capture & Storage (CCS) and CC & Utilization (CCU) technologies to reduce carbon dioxide. CCUS technology is recognized as an effective GHG mitigation measure, but faces high investment costs, the potential for release of toxic collectors to air, and low technology maturity. Also, from an energy and climate policy perspective, CCUS provides a means to substantially reduce greenhouse gas emissions, but there are many complementary aspects to the realization of technology. Therefore, it is required to develop a new concept of breakthrough technology that more efficiently captures, stores and utilizes carbon dioxide.

As a prior art document related to the technical field of the present invention, Japanese Patent Application Laid-Open No. 10-2015-0091834 discloses a liquid crystal display comprising a liquid cathode portion containing a sodium mixed solution solution and a cathode impregnated in a sodium-containing solution; An anode portion including a liquid organic electrolyte, an anode impregnated in the liquid organic electrolyte, and a negative electrode active material located on the anode surface; And a solid electrolyte disposed between the cathode portion and the negative portion; And a hydrogen discharging portion connected to the cathode portion and discharging hydrogen generated in the cathode portion during discharging to the outside.

Korean Patent Laid-Open Publication No. 10-2015-0091834 entitled " Carbon Dioxide Collecting Secondary Battery "

An object of the present invention is to provide a water-based secondary battery using carbon dioxide, which is a greenhouse gas, as fuel.

Another object of the present invention is to provide a water-based secondary battery which can produce hydrogen as an environment-friendly fuel while using carbon dioxide as fuel.

Another object of the present invention is to provide a water-based secondary battery which can produce sodium hydrogencarbonate while using carbon dioxide as a fuel.

According to one aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: a cathode portion having an aqueous electrolyte contained in a first containing space and a cathode impregnated in the aqueous electrolyte; An anode portion containing an organic electrolyte contained in a second accommodation space, and an anode impregnated with the organic electrolyte and containing sodium metal; And a solid electrolyte arranged to selectively pass sodium ions between the cathode portion and the anode portion. In the cathode portion during the discharge, a chemical reaction as in the following Reaction Formula 1 occurs by the carbon dioxide supplied from the outside ,

[Reaction Scheme 1]

CO ₂ (g) + H ₂ O (1)? HCO ₃ ^- (aq) + H ⁺ (aq)

At the cathode portion during the discharge, an electrical reaction as shown in the following Reaction Formula 2 occurs,

[Reaction Scheme 2]

2H ⁺ (aq) + 2e ^- ? H ₂ (g)

At the anode part during the discharge, an electrical reaction occurs as shown in the following reaction formula (3)

[Reaction Scheme 3]

2Na (s) ^- > 2Na ⁺ (aq) + 2e ^-

The total reaction at the time of discharging is provided as in the following [Reaction Scheme 4].

[Reaction Scheme 4]

2 Na (s) + ₂ CO ₂ (g) + 2H ₂ O (1)? ₂ NaHCO ₃ (aq) + H ₂ (g)

The water-based electrolyte is a neutral electrolyte. In the cathode portion during the charging, a reaction as shown in the following Reaction Formula 5 occurs,

[Reaction Scheme 5]

2H ₂ O (1)? O ₂ (g) + 4H ⁺ (aq) + 4e ^-

At the time of charging, a reaction as shown in the following Reaction Scheme 6 occurs at the anode portion,

[Reaction Scheme 6]

Na ⁺ (aq) + e ^- ? Na (s)

The total reaction at the time of charging can occur as in the following [Reaction Scheme 7].

[Reaction Scheme 7]

_{^{4Na + (aq) + 2H 2}} O (l) → O 2 (g) + 4H + (aq) + 4Na (s)

The water-based electrolyte is a basic electrolyte. In the cathode portion during the charging, a reaction as shown in the following Reaction Formula 8 occurs,

[Reaction Scheme 8]

4OH ^- (aq) ^- > O ₂ (g) + 2H ₂ O (1) + 4e ^-

At the time of charging, a reaction as shown in the following Reaction Formula 9 occurs at the anode portion,

[Reaction Scheme 9]

Na ⁺ (aq) + e ^- ? Na (s)

The overall reaction at the time of charging can occur as in the following [Scheme 10].

[Reaction Scheme 10]

^{4Na + (aq) + 4OH -} (aq) → O 2 (g) + 2H 2 O (l) + 4Na (s)

The above-mentioned water-based electrolyte is seawater. In the cathode portion during the charging, reactions as shown in the following Reaction Scheme 8 and Reaction Scheme 11 occur,

[Reaction Scheme 8]

4OH ^- (aq) ^- > O ₂ (g) + 2H ₂ O (1) + 4e ^-

[Reaction Scheme 11]

_{^{2Cl - (aq) → Cl 2}} (g) + 2e -

At the time of charging, a reaction as shown in the following Reaction Scheme 12 occurs at the anode portion,

[Reaction Scheme 9]

Na ⁺ (aq) + e ^- ? Na (s)

The overall reaction at the time of charging can take place as in the following [Scheme 10] and [Reaction Scheme 13].

[Reaction Scheme 10]

^{4Na + (aq) + 4OH -} (aq) → O 2 (g) + 2H 2 O (l) + 4Na (s)

[Reaction Scheme 13]

^{2Na + (aq) + 2Cl -} (aq) → Cl 2 (g) + 2Na (s)

According to another aspect of the present invention, there is provided an aqueous secondary battery in which carbon dioxide is used as a raw material and hydrogen is generated in a discharge process. A reformer for producing hydrogen-rich reformed gas from the hydrogen-containing fuel and generating carbon dioxide as a by-product; A fuel cell supplied with the reformed gas produced from the reformer as fuel; And a carbon dioxide supply unit for supplying carbon dioxide generated in the reformer to the water-based secondary battery, wherein the water-based secondary battery is the water-based secondary battery according to claim 1.

According to another aspect of the present invention, there is provided a water-based secondary battery in which carbon dioxide is used as a raw material and hydrogen is generated in a discharge process. A reformer for producing a hydrogen-rich reformed gas from the hydrogen-containing fuel; A fuel cell supplied with the reformed gas produced from the reformer as fuel; And a hydrogen supply unit for supplying hydrogen generated in the water-based secondary cell to the fuel of the fuel cell, wherein the water-based secondary battery is the water-based secondary battery according to claim 1.

According to another aspect of the present invention, there is provided a water-based secondary battery in which carbon dioxide is used as a raw material and hydrogen is generated in a discharge process. A reformer for producing hydrogen-rich reformed gas from the hydrogen-containing fuel and generating carbon dioxide as a by-product; A fuel cell supplied with the reformed gas produced from the reformer as fuel; A carbon dioxide supply unit for supplying carbon dioxide generated in the reformer to the water-based secondary battery; And a hydrogen supply unit for supplying hydrogen generated in the water-based secondary cell to the fuel of the fuel cell, wherein the water-based secondary battery is the water-based secondary battery according to claim 1.

According to the present invention, all of the objects of the present invention described above can be achieved. Specifically, by using sodium metal as the anode electrode and supplying carbon dioxide to the aqueous electrolyte in which the cathode electrode is immersed, sodium ions migrate through the electrolyte from the anode electrode and react with carbon dioxide in the aqueous electrolyte to form hydrogen and carbonic acid It generates sodium hydrogen and generates electricity.

1 is a schematic diagram illustrating a discharge process of a water-based secondary battery according to an embodiment of the present invention.
FIG. 2 is a schematic view showing the charging process of the water-based secondary cell shown in FIG. 1, and is a view for explaining a case where the aqueous electrolyte used in the cathode is a neutral electrolyte.
FIG. 3 is a schematic view showing a charging process of the water-based secondary battery shown in FIG. 1, and is a view for explaining a case where the aqueous electrolyte used in the cathode portion is a basic electrolyte.
FIG. 4 is a schematic view showing a charging process of the water-based secondary battery shown in FIG. 1, and explains a case where the aqueous electrolyte used in the cathode is seawater.
FIG. 5 is a view showing a schematic configuration of a hybrid battery system having a water-based secondary cell using carbon dioxide according to an embodiment of the present invention.

Hereinafter, the configuration and operation of the embodiment of the present invention will be described in detail with reference to the drawings.

FIG. 1 shows a configuration of a water-based secondary battery using carbon dioxide according to an embodiment of the present invention. 1, an aquatic rechargeable battery 100 according to an embodiment of the present invention includes a cathode 110, an anode 120, and a cathode 130 disposed between the cathode 110 and the anode 120 And a solid electrolyte 130 interposed therebetween. The water-based secondary battery 100 uses carbon dioxide (CO ₂ ), which is a greenhouse gas, as a raw material in the discharging process. The main feature is that hydrogen (H ₂ ) and sodium hydrogencarbonate (NaHCO ₃ ) As an additional feature.

The cathode 110 includes a water-based electrolyte 111 which is accommodated in a first accommodation space 116, one side of which is partitioned by the solid electrolyte 130, and a cathode 115, which is impregnated into the water-based electrolyte 111 Respectively. The cathode 115 may be carbon paper, carbon fiber, carbon felt, carbon cloth, metal foam, metal thin film, or a combination thereof as an electrode for forming an electric circuit. The cathode 110 is formed with an inlet 112 positioned at a lower portion of the first housing space 116 and an outlet 113 located at an upper portion of the first housing space 116. The aqueous electrolyte 111 and the carbon dioxide used as a raw material in the discharge process are introduced into the first accommodation space 116 through the inlet 112 and the gas generated during the charge and discharge processes through the outlet 113 to the outside . Although not shown, the inlet 112 and the outlet 113 can be selectively opened and closed at appropriate timings by a valve or the like during charging and discharging. The water-based electrolyte 111 contained in the first accommodation space 116 includes a neutral water-based electrolyte, a basic water-based electrolyte, seawater, and the like. The charging reaction formula varies depending on the type of the water-based electrolyte 111, . Also, the discharge reaction formula is the same regardless of the kind of the water-based electrolyte 111, which will be described in detail below.

The cathode portion 110 may further include a catalyst for a chemical reaction. For charging, iridium, ruthenium oxide catalyst and perovskite oxide catalyst can be used so that oxygen generating reaction (OER) can be selectively and smoothly performed. At the time of discharging, at least one of platinum, carbon, and graphene which is also used as an oxygen reduction catalyst so as to selectively reduce carbon dioxide can be used.

The anode portion 120 includes an organic electrolyte 121 accommodated in a second accommodation space 126 having one side partitioned by the solid electrolyte 130 and an anode 125 impregnated into the organic electrolyte 121. The anode 125 is an electrode that constitutes an electric circuit, and sodium ions transferred from the cathode portion 110 are reduced and stored as a sodium metal, and a substance including a sodium metal or a sodium metal so that the stored sodium metal can be oxidized . Although not shown, a negative electrode active material layer may be formed on the surface of the anode 125. In the present embodiment, the anode 125 is described as a material containing a sodium metal, but other metals (e.g., Li, Mg, etc.) other than sodium metal may be used.

The solid electrolyte 130 is disposed between the cathode 110 and the anode 120 in the form of a wall so that both surfaces of the solid electrolyte 130 are surrounded by the aqueous electrolyte 111 and the anode 111, And contacts the organic electrolyte 121 accommodated in the second accommodating space 126 of the housing 120. The solid electrolyte 130 selectively passes only sodium ions between the cathode portion 110 and the anode portion 120. In this embodiment, Na ₃ Zr ₂ Si ₂ PO ₁₂ , which is a NASICON (Na super ion conductor), is formed to effectively transmit sodium ions.

Now, the charging / discharging process of the water-based secondary battery 100 described above as the configuration center will be described in detail.

First, the discharging process will be described as follows. 1, the discharging process of the water-based secondary battery 100 is also shown. Referring to FIG. 1, in the cathode 110, a chemical reaction as shown in the following reaction scheme 1 is performed.

[Reaction Scheme 1]

CO ₂ (g) + H ₂ O (1)? HCO ₃ ^- (aq) + H ⁺ (aq)

That is, in the cathode unit 110, carbon dioxide (CO ₂ ) supplied to the cathode unit 110 reacts with hydrogen (HCO ₃ ^- ) and hydrogen cations (H ⁺ ) through spontaneous chemical reaction with water (H ₂ O) Is generated.

In the cathode portion 110, an electrical reaction as shown in the following Reaction Scheme 2 is performed.

[Reaction Scheme 2]

2H ⁺ (aq) + 2e ^- ? H ₂ (g)

That is, in the cathode 110, hydrogen cations H ⁺ receive electrons e ^- , and hydrogen (H ₂ ) gas is generated.

Then, in the anode portion 120, an electrical reaction as shown in the following Reaction Formula 3 is performed.

[Reaction Scheme 3]

2Na (s) ^- > 2Na ⁺ (aq) + 2e ^-

That is, in the anode unit 120, sodium (Na) is decomposed into sodium cations (Na ⁺ ) and electrons (e ^- ) and sodium cations (Na ⁺ ) are delivered to the cathode unit 110 by the solid electrolyte 130 do.

As a result, the overall reaction in the discharge process is as shown in the following [Reaction Scheme 4].

[Reaction Scheme 4]

2 Na (s) + ₂ CO ₂ (g) + 2H ₂ O (1)? ₂ NaHCO ₃ (aq) + H ₂ (g)

That is, the bicarbonate (HCO ₃ ^- ) remaining in the aqueous electrolyte 111 is electronically equilibrated with the sodium cation (Na ⁺ ) migrating from the anode portion 120 to the cathode portion 110, and sodium bicarbonate (NaHCO ₃ ) And hydrogen (H ₂ ) are produced. The generated sodium hydrogencarbonate (NaHCO ₃ ) is present in the aqueous electrolyte 111 in the form of an aqueous solution, and the generated hydrogen gas (H ₂ ) is discharged to the outside through the discharge port 113.

The reaction formula of the discharge process described above is the same regardless of the kind of the water-based electrolyte 111, but the reaction formula of the charging process depends on the type of the water-based electrolyte 111. Hereinafter, the reaction formula of the charging process according to the kind of the water-based electrolyte 111 will be described with reference to FIG. 2 to FIG.

2 is a view for explaining a charging reaction when the aqueous electrolyte 111 is a neutral electrolyte. Referring to FIG. 2, in the cathode portion 110, the following reaction is performed.

[Reaction Scheme 5]

2H ₂ O (1)? O ₂ (g) + 4H ⁺ (aq) + 4e ^-

That is, in the cathode 110, water (H ₂ O) is decomposed by a chemical reaction to generate oxygen gas (O ₂ ), hydrogen cations (H ⁺ ), and electrons (e ^- ). The generated oxygen gas O ₂ is discharged to the outside through the discharge port 113 and the generated hydrogen cations H ⁺ are present in the aqueous electrolyte 111 in the form of an aqueous solution. The generated electrons e ^- And moves to the anode section 120 through the electric circuit.

Further, in the anode portion 120, the reaction shown in the following Reaction Scheme 6 is performed.

[Reaction Scheme 6]

Na ⁺ (aq) + e ^- ? Na (s)

That is, sodium ions (Na ⁺ ) and electrons (e ^- ) transferred from the cathode unit 110 are combined and reduced to sodium metal.

As a result, when a neutral aqueous electrolyte is used, the overall reaction in the charging process is as shown in the following Reaction Scheme 7.

[Reaction Scheme 7]

_{^{4Na + (aq) + 2H 2}} O (l) → O 2 (g) + 4H + (aq) + 4Na (s)

3 is a view for explaining a charging reaction when the aqueous electrolyte used in the cathode portion is a basic electrolyte. Referring to FIG. 3, in the cathode portion 110, the following reaction is carried out as shown in Reaction Scheme 8 below.

[Reaction Scheme 8]

4OH ^- (aq) ^- > O ₂ (g) + 2H ₂ O (1) + 4e ^-

That is, in the cathode portion 110, the hydroxide anion (OH ^- ) is decomposed by the chemical reaction to generate oxygen gas (O ₂ ), water (H ₂ O), and electrons (e ^- ). The generated oxygen gas O ₂ is discharged to the outside through the discharge port 113 and the generated electrons e ^- are transferred to the anode unit 120 through the electric circuit.

Further, in the anode portion 120, the reaction shown in the following Reaction Scheme 9 is carried out.

[Reaction Scheme 9]

Na ⁺ (aq) + e ^- ? Na (s)

That is, sodium ions (Na ⁺ ) and electrons (e ^- ) transferred from the cathode unit 110 are combined and reduced to sodium metal.

As a result, when a basic aqueous electrolyte is used, the overall reaction in the charging process is as shown in the following Reaction Scheme (10).

[Reaction Scheme 10]

^{4Na + (aq) + 4OH -} (aq) → O 2 (g) + 2H 2 O (l) + 4Na (s)

4 is a view for explaining the charging reaction when the aqueous electrolyte used in the cathode portion is seawater. When the aqueous electrolyte is seawater, since the seawater is weakly alkaline and the chlorine anion (Cl ^- ) and the hydroxide anion (OH ^- ) coexist, the reaction (Reaction Scheme 8, Reaction Scheme 9, ]) And the reaction described below with reference to FIG. 4 can occur at the same time.

Referring to FIG. 4, in the cathode portion 110, the following reaction is performed as in the following Reaction Scheme 11.

[Reaction Scheme 11]

_{^{2Cl - (aq) → Cl 2}} (g) + 2e -

That is, in the cathode unit 110, the chlorine anion (Cl ^- ) is decomposed by a chemical reaction to generate chlorine gas (Cl ₂ ) and electrons (e ^- ). The generated chlorine gas (Cl ₂ ) is discharged to the outside through the discharge port 113, and the generated electrons (e ^- ) are transferred to the anode unit 120 through the electric circuit.

In the anode part 120, the reaction shown in the following reaction formula (12) is carried out.

[Reaction Scheme 12]

Na ⁺ (aq) + e ^- ? Na (s)

That is, sodium ions (Na ⁺ ) and electrons (e ^- ) transferred from the cathode unit 110 are combined and reduced to sodium metal.

As a result, when seawater is used as a water-based electrolyte, the overall reaction in the charging process is as shown in the following [Reaction Scheme 13].

[Reaction Scheme 13]

^{2Na + (aq) + 2Cl -} (aq) → Cl 2 (g) + 2Na (s)

FIG. 5 is a view showing a schematic configuration of a hybrid battery system having a water-based secondary cell using carbon dioxide according to an embodiment of the present invention. 5, the complex cell system 1000 according to one embodiment of the present invention-aqueous secondary battery that is the hydrogen gas (H ₂₎ generated in the discharge and the discharge process using a carbon dioxide gas (CO ₂₎ as a starting material ( A reformer 300 for producing hydrogen-rich reformed gas from the hydrogen-containing fuel and additionally generating carbon dioxide gas (CO ₂ ), a fuel cell 200 for producing electricity using hydrogen and oxygen, A carbon dioxide supply unit 400 for supplying carbon dioxide gas generated in the reformer 300 to the water secondary battery 100, a hydrogen supply unit 500 for supplying hydrogen gas generated in the water secondary battery 100 to the fuel cell, And a reformed gas supply unit 600 for supplying the reformed gas produced in the reformer 300 to the fuel cell 200.

The water-based secondary battery 100 is a water-based secondary battery 100 described above with reference to FIGS. 1 to 4. As described in detail with reference to FIG. 1, in the discharge process, carbon dioxide gas is used as a raw material, . The carbon dioxide gas supplied to the water-based secondary battery 100 is carbon dioxide gas generated in the reformer 300 and supplied through the carbon dioxide supply unit 400. The hydrogen gas generated in the water-based secondary battery 100 is supplied to the fuel cell 200 by the water supply and supply unit 500.

The reformer 300 produces hydrogen-rich reformed gas from the hydrogen-containing fuel and additionally generates carbon dioxide gas. For this purpose, in the present embodiment, the reformer 300 is a methane-steam reformer that produces hydrogen (H ₂ ) by the reforming reaction of methane (CH ₄ ) and water vapor (H ₂ O).

 The methane-steam reformer 300 takes up a considerable portion of the hydrogen production process due to its advantages of low process costs and mass production capability. The following Scheme 14 relates to the reforming reaction of the methane-steam reformer 300.

[Reaction Scheme 14]

CH ₄ + H ₂ O -> CO + 3H ₂

CO + H ₂ O - > CO ₂ + H ₂

That is, carbon monoxide (CO) and hydrogen are produced by the chemical reaction between methane and water vapor, and hydrogen can be finally produced by the chemical reaction between carbon monoxide and water vapor continuously. The hydrogen produced in the methane-steam reformer 300 is supplied to the fuel cell 110 or the like by the reformed gas supply unit 600.

However, the methane-steam reformer 300 has many advantages as described above. However, as shown in Reaction Scheme 14, it is necessary to supply steam from the outside for the operation of the process, There is a problem that carbon dioxide, which is a main cause of environmental problems, is generated. However, in the present invention, instead of the carbon dioxide generated in the methane-steam reformer 300 being discharged into the atmosphere or transferred to the separate carbon dioxide capture and storage process, the carbon dioxide supplier 400 for discharging reaction of the water- It is possible to solve the problem of generation of carbon dioxide which is a necessary pit in the operation of the methane-steam reformer 300 by not only transferring the water-based secondary battery 100 to the water-based secondary battery 100, The redundant process can be omitted. Since the methane-steam reformer 300 is a well-known technology, detailed description thereof will be omitted.

The fuel cell 200 generates water by chemical reaction between hydrogen and oxygen, and generates electrical energy. The fuel cell 200 has many advantages in terms of environment friendliness, but it must receive hydrogen extracted from the methane-steam reformer 300 and the like. However, in the case of the present invention, since the fuel cell 200 is constructed as one system with the water-based secondary battery 100, the efficiency is remarkably improved by receiving the hydrogen gas generated in the discharge process of the water-based secondary battery 100 .

The carbon dioxide supplying unit 400 supplies the carbon dioxide gas generated as a by-product in the reformer 300 to the water-based secondary battery 100.

The hydrogen supply unit 500 supplies hydrogen gas generated as a by-product in the discharge process of the water-based secondary battery 100 to the fuel of the fuel cell 200.

The reformed gas supply unit 600 supplies reformed gas produced by the reformer 300 to the fuel of the fuel cell 200.

Although the present invention has been described with reference to the above embodiments, the present invention is not limited thereto. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

100: Water-based secondary battery 110:
111: aqueous electrolyte 112: inlet
113: outlet 115: cathode
120: anode part 121: organic electrolyte
125: anode 130: solid electrolyte
200: fuel cell 300: reformer
400: carbon dioxide supply part 500: hydrogen supply part
600: reforming gas supply part 1000: composite battery system

Claims (14)

A water-based secondary battery in which carbon dioxide is used as a raw material for discharging and hydrogen is generated during discharging;
A reformer for producing hydrogen-rich reformed gas from the hydrogen-containing fuel and generating carbon dioxide as a by-product;
A fuel cell supplied with the reformed gas produced from the reformer as fuel; And
And a carbon dioxide supply unit for supplying carbon dioxide generated in the reformer to the water-based secondary battery,
In the water-based secondary battery,
A cathode portion having an aqueous electrolyte contained in the first accommodation space and a cathode impregnated in the aqueous electrolyte;
An anode portion containing an organic electrolyte contained in a second accommodation space, and an anode impregnated with the organic electrolyte and containing sodium metal; And
And a solid electrolyte arranged to selectively pass sodium ions between the cathode portion and the anode portion,
During the discharge, a chemical reaction as shown in the following Reaction Scheme 1 occurs in the cathode portion by the carbon dioxide supplied from the outside,
[Reaction Scheme 1]
CO ₂ (g) + H ₂ O (1)? HCO ₃ ^- (aq) + H ⁺ (aq)
At the cathode portion during the discharge, an electrical reaction as shown in the following Reaction Formula 2 occurs,
[Reaction Scheme 2]
2H ⁺ (aq) + 2e ^- ? H ₂ (g)
At the anode part during the discharge, an electrical reaction occurs as shown in the following reaction formula (3)
[Reaction Scheme 3]
2Na (s) ^- > 2Na ⁺ (aq) + 2e ^-
The overall reaction at the time of discharge occurs as in the following [Reaction 4].
[Reaction Scheme 4]
2 Na (s) + ₂ CO ₂ (g) + 2H ₂ O (1)? ₂ NaHCO ₃ (aq) + H ₂ (g) The method according to claim 1,
Wherein the aqueous electrolyte is a neutral electrolyte,
At the cathode portion during charging, the reaction as shown in the following Reaction Scheme 5 occurs,
[Reaction Scheme 5]
2H ₂ O (1)? O ₂ (g) + 4H ⁺ (aq) + 4e ^-
At the time of charging, a reaction as shown in the following Reaction Scheme 6 occurs at the anode portion,
[Reaction Scheme 6]
Na ⁺ (aq) + e ^- ? Na (s)
The overall reaction at the time of charging takes place as in the following [Reaction Scheme 7].
[Reaction Scheme 7]
_{^{4Na + (aq) + 2H 2}} O (l) → O 2 (g) + 4H + (aq) + 4Na (s) The method according to claim 1,
The aqueous electrolyte is a basic electrolyte,
At the cathode portion during the charging, the reaction as shown in the following Reaction Scheme 8 occurs,
[Reaction Scheme 8]
4OH ^- (aq) ^- > O ₂ (g) + 2H ₂ O (1) + 4e ^-
At the time of charging, a reaction as shown in the following Reaction Formula 9 occurs at the anode portion,
[Reaction Scheme 9]
Na ⁺ (aq) + e ^- ? Na (s)
The overall reaction upon charging occurs as in the following [Reaction Scheme 10].
[Reaction Scheme 10]
^{4Na + (aq) + 4OH -} (aq) → O 2 (g) + 2H 2 O (l) + 4Na (s) The method according to claim 1,
Wherein the aqueous electrolyte is seawater,
At the cathode portion during the charging, reactions as shown in the following Reaction Scheme 8 and Reaction Scheme 11 occur,
[Reaction Scheme 8]
4OH ^- (aq) ^- > O ₂ (g) + 2H ₂ O (1) + 4e ^-
[Reaction Scheme 11]
_{^{2Cl - (aq) → Cl 2}} (g) + 2e -
At the time of charging, a reaction as shown in the following Reaction Scheme 12 occurs at the anode portion,
[Reaction Scheme 9]
Na ⁺ (aq) + e ^- ? Na (s)
The overall reaction upon charging occurs as in the following [Reaction Scheme 10] and [Reaction Scheme 13].
[Reaction Scheme 10]
^{4Na + (aq) + 4OH -} (aq) → O 2 (g) + 2H 2 O (l) + 4Na (s)
[Reaction Scheme 13]
^{2Na + (aq) + 2Cl -} (aq) → Cl 2 (g) + 2Na (s) The method according to claim 1,
Wherein the cathode includes an inlet through which carbon dioxide is supplied to the first containing space and an outlet through which hydrogen generated in a discharge process is discharged. The method according to claim 1,
Wherein a catalyst for selectively reducing the carbon dioxide is used for discharging the cathode, and at least one of platinum, carbon, and graphene is used as the catalyst. The method according to claim 1,
And a ruthenium oxide catalyst or a perovskite oxide catalyst is used for the oxygen generating reaction (OER) in the cathode. The method according to claim 1,
Wherein the solid electrolyte is formed of Na ₃ Zr ₂ Si ₂ PO ₁₂ . delete The method according to claim 1,
Wherein the reformer is a methane-steam reformer that produces hydrogen (H ₂ ) by a reforming reaction of methane (CH ₄ ) and water vapor (H ₂ O). The method according to claim 1,
And a hydrogen supply unit for supplying hydrogen generated in the water-based secondary battery to the fuel of the fuel cell. A water-based secondary battery in which carbon dioxide is used as a raw material for discharging and hydrogen is generated during discharging;
A reformer for producing a hydrogen-rich reformed gas from the hydrogen-containing fuel;
A fuel cell supplied with the reformed gas produced from the reformer as fuel; And
And a hydrogen supply unit for supplying hydrogen generated in the water-based secondary battery to the fuel of the fuel cell,
The water-based secondary battery,
In the water-based secondary battery,
A cathode portion having an aqueous electrolyte contained in the first accommodation space and a cathode impregnated in the aqueous electrolyte;
An anode portion containing an organic electrolyte contained in a second accommodation space, and an anode impregnated with the organic electrolyte and containing sodium metal; And
And a solid electrolyte arranged to selectively pass sodium ions between the cathode portion and the anode portion,
During the discharge, a chemical reaction as shown in the following Reaction Scheme 1 occurs in the cathode portion by the carbon dioxide supplied from the outside,
[Reaction Scheme 1]
CO ₂ (g) + H ₂ O (1)? HCO ₃ ^- (aq) + H ⁺ (aq)
At the cathode portion during the discharge, an electrical reaction as shown in the following Reaction Formula 2 occurs,
[Reaction Scheme 2]
2H ⁺ (aq) + 2e ^- ? H ₂ (g)
At the anode part during the discharge, an electrical reaction occurs as shown in the following reaction formula (3)
[Reaction Scheme 3]
2Na (s) ^- > 2Na ⁺ (aq) + 2e ^-
The overall reaction at the time of discharge occurs as in the following [Reaction 4].
[Reaction Scheme 4]
2 Na (s) + ₂ CO ₂ (g) + 2H ₂ O (1)? ₂ NaHCO ₃ (aq) + H ₂ (g) A water-based secondary battery in which carbon dioxide is used as a raw material for discharging and hydrogen is generated during discharging;
A reformer for producing hydrogen-rich reformed gas from the hydrogen-containing fuel and generating carbon dioxide as a by-product;
A fuel cell supplied with the reformed gas produced from the reformer as fuel;
A carbon dioxide supply unit for supplying carbon dioxide generated in the reformer to the water-based secondary battery; And
And a hydrogen supply unit for supplying hydrogen generated in the water-based secondary battery to the fuel of the fuel cell,
In the water-based secondary battery,
A cathode portion having an aqueous electrolyte contained in the first accommodation space and a cathode impregnated in the aqueous electrolyte;
An anode portion containing an organic electrolyte contained in a second accommodation space, and an anode impregnated with the organic electrolyte and containing sodium metal; And
And a solid electrolyte arranged to selectively pass sodium ions between the cathode portion and the anode portion,
During the discharge, a chemical reaction as shown in the following Reaction Scheme 1 occurs in the cathode portion by the carbon dioxide supplied from the outside,
[Reaction Scheme 1]
CO ₂ (g) + H ₂ O (1)? HCO ₃ ^- (aq) + H ⁺ (aq)
At the cathode portion during the discharge, an electrical reaction as shown in the following Reaction Formula 2 occurs,
[Reaction Scheme 2]
2H ⁺ (aq) + 2e ^- ? H ₂ (g)
At the anode part during the discharge, an electrical reaction occurs as shown in the following reaction formula (3)
[Reaction Scheme 3]
2Na (s) ^- > 2Na ⁺ (aq) + 2e ^-
The overall reaction at the time of discharge occurs as in the following [Reaction 4].
[Reaction Scheme 4]
2 Na (s) + ₂ CO ₂ (g) + 2H ₂ O (1)? ₂ NaHCO ₃ (aq) + H ₂ (g) 14. The method of claim 13,
Wherein the reformer is a methane-steam reformer that produces hydrogen (H ₂ ) by a reforming reaction of methane (CH ₄ ) and water vapor (H ₂ O).

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