KR102304054B1 - A device seperating and collecting gas without membrane - Google Patents

Abstract

In the artificial leaf device of the present invention, when the artificial leaf device is floated on water, the battery part is exposed on the water, and the electrode part is present in the water, so that the light to be used for the artificial leaf device is absorbed by water and is lost in water while reducing the process Electrolysis may proceed by the electrode part.
In addition, the electrode part is modified with a liquid-infused slippery porous surface (SLIPS), and the liquid-injected slippery porous surface has adequate aerobicity, so hydrogen and oxygen generated by electrolysis do not escape without SLIPS It can travel along the gas wall of the bed and be trapped.

Description

A DEVICE SEPERATING AND COLLECTING GAS WITHOUT MEMBRANE

The present invention relates to a membrane-free gas separation and capture device.

As the world's population explodes, great attention is focused on developing alternative fuels to combat the energy crisis. Solar fuels derived from the abundant solar energy transition have received great attention as a clean, sustainable, storable and environmentally friendly resource. Hydrogen obtained from solar water splitting is such a solar fuel. Since Honda and Fujishima _{first discovered the TiO 2} photoelectrochemical cell (PEC) cell, various types of solar water separation methods have been studied to transform diffusive solar energy into chemical energy.

Among many solar fuel devices, photovoltaic (PV)-electrolysis systems have been actively studied due to their high performance and various applications in the field of solar fuel manufacturing. In an early stage, O. Khaselev and JA Turner combined hydrogen and GaAs-GaInAs PV tandem cells with hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrodes in 12.4 % solar-to-hydrogen conversion efficiency was achieved. Due to the high material cost and complex manufacturing process of series PV cells, the series type configuration can be used _{to interconnect thin film PV cells, such as CuInGaSe 2} (CIGS) and perovskite unit cells, into a cost-effective series type PV cell. ) arrays have been proposed. This series arrangement allows easy control of power generation according to the number of interconnected cells, thus optimizing the targeted solar fuel conversion reaction. Therefore, in addition to water separation, PV-electrolysis has great potential to extend its applications to other solar fuel power generation such as _{CO 2} conversion or N _{2 fixation.}

Another important issue of PV electrolysis is the functional design of the system for more convenient and practical use. Nocera et al. demonstrated monolithic and wireless PV-electrolysis, the so-called artificial leaf, by combining a silicon PV tandem cell with an Earth-rich catalyst. Typical artificial leaves have scalability problems associated with extended ion detouring, but these shortcomings can be addressed with a smart, purpose-oriented monolithic module design. For example, a multi-purpose artificial leaf design that can be applied to various environments with planar and floating characteristics has been proposed. These unique properties provide artificial leaves with useful features such as short ion pathways, buoyancy, recyclability and scalability.

Despite significant improvements in module performance and functionality, it still does not solve the important problems associated with the separation and collection of product gases in water separation. In the monolithic PV-electrolysis module of the present invention, the H ₂ gas product is necessarily mixed with the corresponding product, O ₂ gas. Therefore, additional energy and process for product separation are required to obtain _{pure H 2 gaseous fuel.} Classical electrolysis systems have solved this problem with ion exchange membranes, but these membrane systems account for more than 40% of the capital cost ^{in commercial electrolysis systems (1,000 -1,500 $ KW -1 ).} In addition, there are some practical limitations to its application to small and monolithic devices. In addition to requiring complex and expensive manufacturing processes, membrane systems introduce durability problems associated with contamination and corrosion of complex systems. So far, several attempts have been made to develop membrane-less modules utilizing various driving forces for kinetic gas separation, but these have additional external energy transfer convective flows, very complex modules, which greatly limit the practical use of monolithic artificial leaf devices. It requires design and strictly controlled conditions.

In the present invention, we have invented a simple but effective gas separation system based on a very compact monolithic PV electrolysis device that can manipulate and selectively collect gas bubbles without membranes or external energy. Through biomimetic surface modification, the HER/OER electrode showed highly efficient gas bubble trapping, transport and collection of _{H 2} and O ₂ with a gas trapping efficiency of greater than 90% and high purity. To manipulate electrolysis product gas bubbles, a slippery liquid infused porous surface (SLIPS) biomimicking a pitcher-plant for modification of the HER/OER electrode of a PV-electrolysis system this is used _{As H 2} and O ₂ gases are generated at each of the HER and OER electrodes, the buoyancy forces them to move upward along each inclined electrode surface. In these processes, biomimetic SLIPS walls deposited on the side edge of each electrode trap and transport gas bubbles to a collection port, preventing leakage of gas bubbles from the electrode surface. Due to the design and characteristics of the inclined SLIPS electrodes, the generated H ₂ and O ₂ gases can be selectively collected at each product port without crossover or loss. This simple and efficient gas separation capability also applies to certain monolithic PV-electrolysis systems in which inclined SLIPS-modified HER/OER electrodes are _{combined with interconnected CuInS 2 (CIS) PVs.} In addition, these unique artificial leaves without membranes can float on the water surface with enclosed free space inside, providing additional advantages such as overall lighting utilization and reusability.

KR 10-1952154

In the present invention

As an artificial leaf device that can be operated by floating on water,

a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of water by using light energy; and

a hydrogen generating electrode unit receiving electric potential from the battery unit to decompose water through electrolysis and an electrode unit generating oxygen gas; Including, two electrode parts are connected to both ends of the battery part at the lower end of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,

The electrode part has a slippery liquid infused porous surface to collect hydrogen gas or oxygen gas generated from water electrolysis,

The deposition layer constituting the battery unit is provided to face inside the triangular structure,

A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the water,

It aims to provide an artificial leaf device.

Another object of the present invention is to provide a method for collecting hydrogen gas using the artificial leaf device.

Another object of the present invention is to provide a method for collecting oxygen gas using the artificial leaf device.

In addition, in the present invention, as an artificial leaf device that can be operated by floating on a liquid,

a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of a liquid by using light energy; and

an oxidation electrode unit and a reduction electrode unit receiving a potential from the battery unit and decomposing the liquid through electrolysis; including,

At the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,

One of the two electrode parts is a cathode, the other is an anode,

The electrode part has a slippery liquid infused porous surface so as to collect the gas generated from the electrolysis of the liquid,

The deposition layer constituting the battery unit is provided to face inside the triangular structure,

A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the liquid,

It aims to provide an artificial leaf device.

One aspect of the present invention for achieving the above object is

As an artificial leaf device that can be operated by floating on water,

a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of water by using light energy; and

a hydrogen generating electrode unit receiving electric potential from the battery unit to decompose water through electrolysis and an electrode unit generating oxygen gas; including,

At the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,

The electrode part has a slippery liquid infused porous surface so as to collect hydrogen gas or oxygen gas generated from water electrolysis,

The deposition layer constituting the battery unit is provided to face inside the triangular structure,

A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the water,

artificial leaf device.

The artificial leaf device can be photoelectrolyzed in a variety of natural environments that are not clean due to water scarcity and floating as well as water-rich and clear environments, and can be recycled after use and can be easily recovered to prevent environmental pollution. It is formed into a practical and functional structure.

In the artificial leaf device, when the artificial leaf device is floated on water, the battery part is exposed on the water, and the electrode part is present in the water, thereby reducing the process in which the light to be used for the artificial leaf device is absorbed and lost in water. Electrolysis may proceed by part.

In addition, the artificial leaf device can collect, transport and collect hydrogen gas and oxygen gas generated by electrolysis without crossover through two electrodes having a slippery liquid infused porous surface. have.

The battery unit may be a series type solar cell in which at least two or more superstrate type solar cell unit units are connected.

Accordingly, the present invention provides an artificial leaf device that can be used and recovered in various aquatic environments regardless of the amount and transparency of water. 4b is a schematic diagram showing an artificial leaf device according to an embodiment of the present invention.

The artificial leaf device according to the present invention includes a battery unit that provides a potential required for electrolysis using light energy, and an electrode unit that receives a potential from the battery unit and generates hydrogen gas and oxygen gas through electrolysis of water.

The cell unit may use a superstrate-type solar cell or a perovskite-type solar cell as a means for providing an electric potential required for electrolysis by using light energy.

The super-straight solar cell has a structure in which a transparent conductive oxide (TCO) is first formed on a light-transmitting substrate, and then a light absorption layer and a back electrode are formed. Since there is no need to additionally form a protective layer or encapsulation on the transparent electrode, there is an advantage in that the structure is simplified. In addition, the super-straight solar cell has an advantage of being lightweight compared to the substrate-type solar cell in which a back electrode, a light absorption layer, a transparent electrode, and the like are formed on a substrate.

The battery unit includes a light-transmitting substrate, a transparent electrode formed on the light-transmitting substrate, a light absorption layer formed on the transparent electrode, and a rear electrode formed on the light absorption layer. 10 shows a schematic diagram of the structure of a super-straight solar cell according to an embodiment of the present invention.

The light-transmitting substrate is preferably formed of a light-transmitting material capable of transmitting light, and as such a material, glass or a transparent polymer may be used. In addition, since the substrate is exposed to the external environment, it is preferable to be formed of glass having excellent durability against external environments such as gaseous state or contaminants in water.

The transparent electrode is formed of a material having light transmittance and electrical conductivity, such as a transparent conductive oxide, a transparent conductive sulfide, and a transparent conductive nitride, preferably a transparent conductive oxide, more preferably a tin oxide (SnO ₂ ), It is preferable to use zinc oxide (ZnO), indium oxide (InO), indium-containing tin oxide (ITO), or fluorine-containing tin oxide (FTO).

The light absorption layer is a layer that absorbs light energy incident through the light-transmitting substrate. In the case of a super-straight solar cell, the nanostructure core is formed on the transparent electrode to prevent reflection and serves as a window, and the nanostructure core is transparent while covering the core. It is formed on the electrode and includes a nanoshell serving as a buffer layer, and an infiltration layer formed flat on the nanostructure core and the nanoshell to serve as a light absorption layer. The nanostructure core is formed in various nanostructure shapes including rod shapes using _{ZnO, TiO 2 , and SnO.}

The shell is formed of CdS, In(O,S), Zn(O,S), InS, ZnS or CdSe. The infiltration layer 133 is CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe), CuInTe ₂ (CITe), CuGaTe (CGTe), Cu(In,Ga)S (CIGS), Cu(In,Ga)Se(CIGSe), Cu ₂ ZnSnS ₄ (CZTS), and CdTe are formed including one or more selected from the group consisting of. Preferably, _{CuInS 2} (CIS), Cu(In,Ga)S, ^{which has a high light absorption coefficient of 105 cm -1} and a band gap of 1.5 eV and can efficiently form electron-hole pairs by covering the visible light range. (CIGS) or Cu ₂ ZnSnS ₄ (CZTS).

The infiltration layer is CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe), CuInTe ₂ (CITe), CuGaTe (CGTe), Cu (In ,Ga)S(CIGS), Cu(In,Ga)Se(CIGSe), Cu ₂ ZnSnS ₄ (CZTS), and CdTe are formed including one or more selected from the group consisting of. Preferably, _{CuInS 2} (CIS), Cu(In,Ga)S, ^{which has a high light absorption coefficient of 105 cm -1} and a band gap of 1.5 eV and can efficiently form electron-hole pairs by covering the visible light range. (CIGS) or Cu ₂ ZnSnS ₄ (CZTS).

When the light absorption layer is a perovskite solar cell, it is formed on the transparent electrode and covers the nanoparticles of the nanoparticle layer and the nanoparticle layer containing mesoporous particles that function as anti-reflection and windows, and a perovskite layer that absorbs light. include In the case of a perovskite-type solar cell, a hole transport layer is further included on the perovskite layer.

The nanoparticle layer is titanium (Ti), tin (Sn), zinc (Zn), tungsten (W), zirconium (Zr), gallium (Ga), indium (In), yttrium (Y), niobium (Nb), It has a porous structure including nanoparticles having a particle diameter of 10 to 50 nm formed of an oxide of a metal selected from the group consisting of tantalum (Ta), vanadium (V), and combinations thereof.

The perovskite layer is methylammonium lead halide (MAPbX ₃ , X=Cl,Br,I) or formamidinium-based lead halide (FAPbX ₃ , X=Cl,Br) , I) may be formed of a perovskite-based material such as.

The rear electrode is formed of gold (Au), silver (Ag), nickel (Ni), or molybdenum (Mo).

In a specific embodiment, the cell unit is a series of two or more CIS-based solar cells, and the CIS layer of the CIS-based solar cell is located at the top of the cell unit and is exposed on the water when the artificial leaf device is floated on the water. may be done with Preferably, the CIS layer of the CIS-based solar cell may be located at the top of the cell unit.

The battery unit in which at least two or more solar cells are connected in series on one light-transmitting substrate forms a light extraction layer so that a part of the transparent electrode of the solar cell is exposed, and the rear electrode formed on the light extraction layer is adjacent to another solar cell It is preferably formed so as to be connected to the exposed portion of the transparent electrode of the cell.

In the case of using the battery part having the above structure, since the transparent electrode is exposed at one end of the light-transmitting substrate and the back electrode is exposed at the other end, the transparent electrode and the back electrode are easily electrically connected to the electrode part through the conductive member. can be connected

In addition, when the battery unit having the above structure is used, there is an advantage that an additional waterproof treatment is not required on the light active area of the light absorption layer, and the light-transmitting substrate itself plays a waterproof role.

10 is a schematic diagram showing the configuration (a) of the battery unit according to an embodiment of the present invention, the energy band of the cells connected in series (b), the generation and separation of carriers in the light absorption layer, and the transmission path (c) of electrons and holes was shown.

In addition, the electrode part can increase the light conversion efficiency by connecting the perovskite type solar cells in series. 11 shows a schematic diagram of a structure of a perovskite-type solar cell according to an embodiment of the present invention.

The artificial leaf device according to the present invention includes a hydrogen generating electrode unit for decomposing water through electrolysis by receiving a potential from the battery unit and an electrode unit for generating oxygen gas.

The electrode part is a means for generating a chemical through electrolysis by receiving a potential from the battery part, and at the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other. , characterized in that the two electrode parts and the battery part form a triangular structure. In addition, the electrode part may be connected to the lower end of the battery unit, and may be characterized in that it exists in water when the artificial leaf device is floated on the water. Due to the triangular structure, there is an advantage in that the manufacturing process is simple and the artificial leaf device can be formed in a compact size.

The two electrode parts are connected to both ends of the battery part at the lower end of the battery part, the two electrode parts are connected to each other, one of the two electrode parts is a hydrogen generating electrode, and the other is an oxygen generating electrode. The hydrogen generating electrode may be a cathode including a hydrogen generating catalyst layer, and the oxygen generating electrode may be an anode including an oxygen generating catalyst layer.

As the substrate, a substrate formed of a non-conductive material such as glass, plastic, or a polymer-based film such as PET or PI may be used.

The anode is a cathode layer of 50 to 150 nm thick formed including nickel (Ni), cobalt (Co), copper (Cu), molybdenum (Mo), etc. and a material catalyzing hydrogen generation 1 to 5 nm thick. and a hydrogen evolution catalyst layer. In addition, the cathode further includes an adhesive layer with a thickness of 5 to 20 nm formed including titanium (Ti) and the like in order to increase the adhesion of the cathode layer on the substrate.

The hydrogen generation catalyst layer is a noble metal such as platinum (Pt), gold (Au), rhodium (Rh), iridium (Ir), a compound such as CoS, MoS, CoP, or Ni, Mo, Co, Cu, such as NiMo, Co-Mo And using any one or more alloys selected from the group consisting of Fe is formed into a very thin thin film of 2 to 3 nm.

The anode has a thickness of 30 to 40 nm formed including a material that catalyzes oxygen generation and an anode layer of 50 to 150 nm thick formed including nickel (Ni), cobalt (Co), copper (Cu), molybdenum (Mo), etc. and an oxygen evolution catalyst layer. In addition, the anode further includes an adhesive layer with a thickness of 5 to 20 nm formed including titanium (Ti) and the like in order to increase the adhesion of the anode layer on the substrate. In addition, the anode further includes a promoter layer to help oxygen generation, the promoter layer is a noble metal such as platinum (Pt), gold (Au), rhodium (Rh), iridium (Ir), CoS, MoS, CoP, etc. It can be formed into a very thin thin film of 2 to 3 nm using a compound of NiMo, Co-Mo, etc., any one or more alloys selected from the group consisting of Ni, Mo, Co, Cu and Fe.

The oxygen generation catalyst layer is formed to a thickness of 30 to 40 nm using a noble metal oxide such as RuO and IrO, an oxide such as NiO, Co ₃ O ₄ , MnO ₂ , or a doped oxide such as (Ni,Fe)O.

A schematic diagram of a specific artificial leaf device according to the present invention is shown in FIG.

It is preferable that the angle formed by the battery part and the electrode part of the artificial leaf device is 30 degrees, and the length in the direction of the side of the electrode part forming the triangle is 2.6 cm. In one specific embodiment, the angle formed by the battery unit and the oxygen generating electrode and the angle formed by the battery unit and the hydrogen generating electrode are the same, and the length in the direction of the side of the oxygen generating electrode and the hydrogen generating electrode is the same, so that the isosceles battery unit can form an isosceles triangle.

Another aspect of the present invention for achieving the above object is a method for capturing hydrogen, oxygen, or both using the artificial leaf device.

Specifically, the gas collection method using an artificial leaf device according to the present invention may be an oxygen gas collection method using an artificial leaf device, a hydrogen gas collection method using an artificial leaf device, or a method for capturing oxygen and hydrogen gas using an artificial leaf device have. Specifically, the method for capturing hydrogen, oxygen or both of them using an artificial leaf device according to the present invention comprises the steps of: (a) placing the artificial leaf device on water;

(b) performing water electrolysis by irradiating light energy to the artificial leaf device; and

(c) capturing hydrogen, oxygen, or both produced from the water electrolysis.

In step (a), when the artificial leaf device is placed on water, the battery part floats on the water due to the light density of the substrate constituting the artificial leaf device, and the two electrode parts are placed in water to perform electrolysis.

In step (b), the artificial leaf device is irradiated with light energy so that the battery located in the battery unit absorbs the light energy and provides an electric potential to the electrode unit. The electrode unit receiving the electric potential may be positioned in water to perform water electrolysis in water. The light energy may preferably be solar energy.

The step (c) includes capturing hydrogen, oxygen, or both produced from the water electrolysis. Of the electrode parts, the hydrogen generating electrode may collect only hydrogen without crossover, and the oxygen generating electrode may collect only oxygen without crossover. Hydrogen or oxygen gas bubbles moving along the surface of the electrode part modified with a slippery liquid infused porous surface (SLIPS) can be collected at the top of the electrode part without leakage.

The surfaces of the hydrogen-generating electrode and the oxygen-generating electrode are modified with a slippery liquid infused porous surface (SLIPS), and the liquid-injected slippery porous surface has adequate aerobicity, Oxygen can travel along the gas wall on the SLIPS and be captured without escaping. In particular, hydrogen and oxygen can be collected on the hydrogen generating electrode without crossover, and high purity hydrogen and oxygen gas can be collected.

SLIPS was first introduced as a biomimetic of Nepenthes pitcher in 2011 to develop a surface structure that exhibits non-wetting properties for various types of liquids.

The SLIPS used in the present invention is manufactured by filling a lubricating oil into a micro/nano structure with low surface energy. When the lubricating oil of SLIPS comes into contact with external liquids, a slippery interface is formed, and various liquids (water, hydrocarbon, crude oil, blood, etc.) Quickly repairs damage caused by impact. In particular, in the present invention, a micro/nano structure that can stably hold lubricating oil before synthesizing the SLIPS surface was synthesized by spray coating. After _{surface treatment of SiO 2} nanoparticles to make them hydrophobic, they were spray coated to prepare a surface having a microstructure and a nanostructure. Finally, the SLIPS surface was fabricated by penetrating fluorinated oil as a lubricant.

The SLIPS has an intermediate value between the super-hydrophobic surface and the super-hydrophilic surface, so the adhesion of the bubble is ideal for use in controlling the generated bubble. Therefore, when the electrode surface where each gas is generated is tilted in the vertical direction, the gas generated by the buoyancy force moves upward. Through this process, hydrogen gas and oxygen gas can be separated and successfully collected at each HER/OER electrode.

Also, in the present invention

As an artificial leaf device that can be operated by floating on a liquid,

a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of a liquid by using light energy; and

an oxidation electrode unit and a reduction electrode unit receiving a potential from the battery unit and decomposing the liquid through electrolysis; including,

At the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,

One of the two electrode parts is a cathode, the other is an anode,

The electrode part has a slippery liquid infused porous surface so as to collect the gas generated from the electrolysis of the liquid,

The deposition layer constituting the battery unit is provided to face inside the triangular structure,

A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the liquid,

artificial leaf device.

A non-limiting example of the liquid may be any one or more selected from the group consisting of electrolyte, distilled water, tap water, and seawater.

A non-limiting example of the reaction caused by the electrolysis may be an electrolysis reaction of water.

For example, in an embodiment, when the reaction occurring by the electrolysis is an electrolysis reaction of water, the gas generated in the oxidation electrode part is oxygen, and the gas generated in the reduction electrode part is hydrogen.

As described above, the artificial leaf device of the present invention can be used for electrolysis reactions of various reactions, and as a slippery liquid infused porous surface is provided to face the outside of the triangular structure, the oxidation electrode without crossover Different gases may be collected at the upper end of the negative electrode and the reduction electrode.

In the artificial leaf device of the present invention, when the artificial leaf device is floated on water, the battery part is exposed on the water, and the electrode part is present in the water, so that the light to be used for the artificial leaf device is absorbed by water and is lost in water while reducing the process Electrolysis may proceed by the electrode part.

In addition, the electrode part is modified with a liquid-infused slippery porous surface (SLIPS), and the liquid-injected slippery porous surface has adequate aerobicity, so hydrogen and oxygen generated by electrolysis do not escape without SLIPS It can travel along the gas wall of the bed and be trapped.

1 shows an overview of the artificial leaf device of the present invention.
2 shows the results of measuring the water contact angle and bubble contact angle on the biomimetic surface of the artificial leaf device of the present invention, and shows the manner in which bubbles are manipulated on the surface.
Fig. 3 relates to the gas bubble trapping, transport and collection principle in an inclined electrode with a SLIPS gas wall, (a) a schematic diagram of the force acting on the SLIPS gas wall at the side edge of the electrode and the gas bubbles carrying it (α° (b) Schematic diagram of the gas bubble trapping, transporting and collecting functions of the SLIPS gas wall when the electrode is tilted 30 degrees during water separation and 30 degrees horizontally (c) H ₂ /O ₂ generation, separation and (d) H ₂ gas capture efficiency results for electrodes of various configurations (e) showing the purity of _{H 2} /O ₂ gas at each HER/OER collection port. will be.
4 is an image related to the application of the monolithic PV electrolysis artificial leaf device of the present invention, (a) nanostructured CIS cells in series for high photovoltage generation (b) schematic diagram (c) biomimetic modified HER/ Actual driving images of single PV electrolysis equipped with OER electrodes (d) Expected performance of PV electrolysis, cross JV measurement curves of series and two-electrode PV cells set to less than 1.0 M KOH, and actual values of wired PV-electrolysis (e) Practical performance of monolithic PV electrolysis measured with _{collected H 2} /O _{2 gas.}
Figure 5 shows WCA, BCA and gas bubble movement in Ni-Pt electrodes (a) WCA (4.3 ± 1.7 °) (b) underwater BCA (168.8 ± 7.1 °) (c) (i) gas at the HER electrode surface. It shows bubble generation and separation of gas bubbles from the side (ii) and upper edge (iii) of the Ni-Pt electrode when inclined at 40° in 0.1 M KOH with an applied current of 10 mA.
Figure 6 shows the measurement results of bubble adhesion in water of (a) sputtered Ni-Pt electrodes (~100 μN), (b) SHS (not measurable, very high) and (c) SLIPS (~300 μN).
Figure 7 shows the leakage _{of H 2} gas from the top and side of the Ni-Pt electrode.
8 is a graph showing the electrical performance of a single cell and an interconnected battery.\ FIG. 9 is a schematic diagram showing an isosceles triangular structure formed by the battery unit 10 and the electrode unit 20 of the artificial leaf device of the present invention. .
10 is a schematic diagram of a structure of a super-straight solar cell according to an embodiment of the present invention.
11 is a schematic diagram showing the configuration of the battery unit (a), the energy band of the cells connected in series (b), the generation and separation of carriers in the light absorption layer, and the transmission path of electrons and holes (c) according to an embodiment of the present invention; will indicate
12 is a schematic diagram of a structure of a perovskite-type solar cell according to an embodiment of the present invention.

Examples and Experimental Examples

Hereinafter, preferred examples and experimental examples are presented to help the understanding of the present invention. However, the following examples are only applied to understand the present invention more easily, and the content of the present invention is not limited by the examples.

Example 1. Preparation of electrode part substrate

A base electrode was prepared on a glass substrate as is conventionally known. First, the substrate was mask patterned by polyimide tape on the side of the glass on which the biomimetic SLIPS wall was to be deposited. Then, conductive electrodes were prepared by continuous sputtering of Ti (5 nm), Ni (50 nm) and thin film Pt (~ 3 nm) on a patterned substrate for use as a HER electrode in a water electrolysis system. To prepare the OER electrode, OER precursor solution, 45 mM nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ .6(H ₂ O), Sigma-Aldrich, 99.999%), 5 mM iron nitrate hexahydrate (Fe(NO ₃ ) ₂ 9(H ₂ O), Sigma-Aldrich, 99.999%) and Triton X-100 (1500 gmol-1 of metal ions, Sigma-Aldrich) were dissolved in ethanol (Fisher ChemAlert Guide) and at 5000 rpm for 30 seconds A conductive electrode was spin coated. Thereafter, it was annealed on a 300° C. hot plate for 5 minutes. This solution coating and annealing were repeated three times to prepare an optimized OER catalyst layer on the electrode.

Example 2. Preparation of SHS and SLIPS

SiO ₂ (10-20 nm) nanoparticles (2 g, Sigma-Aldrich) were added to dehydrated toluene (40 mL, Samchun, ≥ 99.5 %) with 1 mL of trichloro (octadecyl) silane (Sigma-Aldrich, ≥ 90 %) After dispersion, the mixture was stirred at room temperature for 3 hours. Then, toluene was evaporated at 368K for 5 hours to obtain hydrophobic SiO ₂ nanoparticles, which were then sonicated in 100 mL ethanol (Fisher ChemAlert Guide) to form a suspension. To form a pattern of a biomimetic superhydrophobic surface (SHS) or SLIPS on the electrode, a part of the area was masked, and 3 mL of the suspended SiO ₂ solution was spray coated onto the electrode substrate. For spray coating, the N ₂ gas pressure was maintained at ~20 psi, and the distance between the spray gun and the substrate was fixed at ~10 cm. The coated surface was dried at room temperature for ~5 min to prepare a stable SHS on the substrate. Meanwhile, SLIPS was prepared by infiltrating SHS with fluorinated oil (DuPont Krytox 103) and rinsing with distilled water.

Example 3. Serial CIS PV Cell Fabrication

To fabricate CIS PV cells in series on patterned ITO glass using previously known Yong's method, polyimide tape was pattern-applied onto ITO glass to perform selective layer deposition of window/buffer/adsorption layer. First, a 50 nm ZnO seed layer was sputter deposited on the patterned glass. Then, 10 mM aqueous zinc nitrate hexahydrate (Zn(NO ₃ ) ₂ .6H ₂ O, Sigma-Aldrich, 99.98%) and ammonium hydroxide (2 mL, Sigma-Aldrich, 28-30 wt%, NH _{3 in water)} ), a ZnO NRs window layer was grown by hydrothermal method by placing the substrate in 100 mL of an aqueous solution. A CdS buffer layer was successively deposited on the ZnO NR layer using a nanocrystal layer deposition method. ZnO NRs substrates were placed in an aqueous mixed solution of 10Mm thioacetamide (C ₂ H ₅ NS, Sigma-Aldrich 98.0%) and 10 mM cadmium chloride (CdCl ₂ , Sigma-Aldrich 99.0%) for 1 hour. Then, a CIS absorber layer was deposited from the precursor ink solution coating and annealed. The prepared ink, indium (III) acetate (0.2428 g, In(OAc) ₃ , Sigma-Aldrich 99.99 %), copper iodide (0.1429 g, CuI, Sigma-Aldrich 99.999 %) and thiourea (0.1570 g) were mixed with methanol ( 5mL, CH4O, Sigma-Aldrich, in which the precursor solution dissolved in 99.8%), CH4N2S, Sigma- Aldrich, 99%), butyl amine _{(2mL, C 4 H 9 NH} 2, Sigma-Aldrich, 99.5%) and propionic acid (1ml , C ₂ H ₅ COOH, Sigma-Aldrich, 99.5%) was sprinkled on the ZnO/CdS nanostructure layer and spin-coated at 1300 rpm for 30 s, followed by subsequent annealing steps at 150 °C and 300 °C for 10 min on a hot plate. proceeded. This CIS process was repeated three times to infiltrate the nanostructured layer. After deposition of the CIS absorber layer, the patterned polyimide tape was removed. A gold layer was sputter deposited using a mask, and each of the isolated PV cells was electrically interconnected in series.

Example 4. Assembly of monolithic artificial leaves without membrane

The series CIS PV cells were electrically connected to opposite substrates of two HER/OER electrodes in a beveled configuration by silver paste in series, and encapsulated with rigid polyvinyl chloride (PVC) film and epoxy as shown in Fig. 4b. .

A PVC substrate wall was used to give the module a low density for floatation. The whole module has a hollow inverted triangular structure, where the PV substrate has the CIS layer facing the top of the module and the two ISE substrates are tilted from the bottom and connected to face the biomimetic modified surface. Then, an epoxy is applied to cover the silver connections and crevices, to keep water out and to waterproof the inside of the system.

Experimental Example 1. Characterization of the manufactured artificial leaf device

The contact angle of each sample was measured using a SmartDrop instrument (Femtofab, Korea). To improve the measurement accuracy, contact angles were measured at three locations in each sample while 10 μL of water droplets were used. Samples were immersed in deionized water in a glass bath, 10 μL bubbles were placed on the surface, and the air contact angle was measured with SmartDrop. The adhesion between air and each sample was measured with a laboratory system consisting of a bubble holder, an analytical balance (AS220.R2, Radwag), a motorized stage (Z725B, TDC001, Thorlabs) and a video microscope (AM4115TL, AnMo Electronics). The bubble holder was placed on the analytical balance and the glass bath was placed on the motorized stage. The sample was immersed in a glass bath filled with deionized water and the ring portion of the holder was immersed in the bath. A bubble (10 μL) was attached to the ring. The change in the mass of the holder with the bubble was measured at the same time as the distance between the bubble and the substrate was changed using a motorized stage. Controls and measurements were performed using the Labview program built in the laboratory. The shape of the bubble during the measurement was confirmed using a video microscope. The adhesive force was calculated from the change in the mass of the bubble holder. Water electrolysis was performed by an electrochemical analyzer (Compactstat, IVIUM technology) to control the electrical bias and the resulting data were recorded. The performance characteristics of the series PV cells were tested using AM1's solar simulator (Sun 3000, ABET technology), 5G illumination (100 mW/cm ² ) and an electrochemical analyzer. PV-electrolysis was also evaluated by measuring electrical performance under illumination with a series PV cell electrically connected to an ISE-modified HER/OER electrode in an electrolyte solution. The gas collected at each collection port was sampled with a gas tight syringe (100 μL, Hamilton) and analyzed by gas chromatography (GC 7890 B series, Agilent) with a column (Mol Sieve 5A, SUPELCO). Gas data were computer analyzed (GC Openlab Chemstation Software).

Experimental Example 2. Analysis of bubble behavior for SLIPS-modified electrodes

To identify the optimal design of the biomimetic modified electrode surface, we first studied the bubble behavior for SHS- or SLIPS-modified electrodes. SHS biomimicking lotus leaf was prepared on a glass surface by spray coating a solution of _{pretreated hydrophobic SiO 2} nanoparticles dispersed in ethanol as shown in FIG. 2a. The water contact angle (WCA) of SHS is 158.8 ± 1.2 ° (Fig. 2b), and the underwater bubble contact angle (BCA) is about 0 ° (Fig. 2c), and there are many bubbles, indicating high aerobicity. On the other hand, SLIPS shown in FIG. 2d, which biomimicked Nepenthes cystic plants, was prepared by injecting fluorinated oil into SHS. Due to the low surface energy and nano/microstructure of SHS, the fluorinated oil forms a thermodynamically stable and immobilized lubricant layer, inaccessible to various liquids, resulting in a wettability transition from SHS to SLIPS. SLIPS possessed a WCA of 107.5 ± 0.4° (Fig. 2e) and 75.1 ± 0.3° BCA (Fig. 2f) in water, which exhibited hydrophobicity and aerobicity, respectively. For reference, the wettability of the exposed Ni-Pt sputtered HER electrode surface was also tested, and H ₂ generating gas was actually generated. The results showed that the WCA and water BCA values were 4.3 ± 1.7 ° and 168.8 ± 7.1 °, respectively (Figs. 5a and 5b).

Gas bubbles behave very differently on the three surfaces of water. This is due to the varying adhesion of gas bubbles on the surface. The adhesion of gas bubbles was measured on the HER electrode, SHS and SLIPS surfaces ( FIG. 6 ). SHS had very high and unmeasurable adhesion, whereas SLIPS had moderate bubble adhesion, which was three times higher than that of the exposed HER surface. To monitor and characterize the actual underwater gas bubble motion on the electrode surface with various wettability, we prepared biomimetic SHS or SLIPS adjacent to the HER electrode surface and inclined it as shown in Figures 2g and h. . Since the gas bubbles are forced by buoyancy in water, the gas bubbles generated on the HER electrode moved along the electrode slope towards the biomimetic surface. The main driving force (F _driven ) due to buoyancy is the following equation (1).

where ρ, V, g and α represent the water density, bubble volume, gravitational acceleration and the inclination angle of the substrate, respectively. Two samples were tilted at 40° and a current of 10 mA was applied to each. As shown in FIGS. 2G and 2H , continuous H ₂ gas bubbles were generated on the HER surface. _{As the H 2} gas bubbles generated from the HER electrode migrate towards the SHS, they migrate immediately into the SHS at the Ni-Pt/SHS interface. The rapid transport of bubbles forms an accumulation at the top of the SHS, due to the superaerophilicity and high bubble adhesion of SHS in water. However, excessively high adhesion of gas bubbles on the SHS prevents subsequent gas bubbles from moving to the next collection port. Therefore, it is very difficult to apply SHS to the gas collection system. On the other hand, SLIPS (Fig. 2h) exhibits significantly different bubble behavior from SHS. Because SLIPS is more aerobic than Ni-Pt HER surface and has higher bubble adhesion, H ₂ gas bubbles generated on the HER surface are easily trapped at the interface with SLIPS. As the water separation reaction proceeds, the trapped bubbles accumulate and expand. Then, when the F _driven overcomes the kinetic resistance with the enlarged V, they are transported along the SLIPS. Unlike SHS, SLIPS is not overly aerobic, so bubbles can retain their shape and move steadily to the top of the surface. After repeating this process, the uppermost bubbles coalesce until the buoyancy is greater than the bubble adhesion of the SLIPS, and the bubbles are easily separated from the top of the electrode. Both SHS and SLIPS have bubble collection and transport functions, but only SLIPS allows easy bubble separation. The moderate bubble adhesion of SLIPS is advantageous for gas transport and collection without separation/loss, and for product collection without delay.

Experimental Example 3. Analysis of gas bubble collection results

Based on the underwater gas bubble motion results shown in Fig. 2, we adopted a SLIPS pattern design on the electrode surface to help efficient product gas separation and collection. In the case of the exposed Ni-Pt electrode, continuous gas bubble leakage was observed at the side edges due to the low bubble adhesion, which inevitably leads to high losses in the collection process and crossover of the product (Fig. 5c). However, with the smartly designed SLIPS gas wall, the gas bubble affinity is high, keeping the escapeable gas bubbles safe. As shown in the schematic of FIG. 3A , a 2 mm wide SLIPS-modified gas wall strip was prepared on the side edge of the electrode. The role of the SLIPS gas wall is to block the leakage of gas bubbles through collection of gas bubbles (bubble 1) and transport the bubbles to the collection port on top of the electrode. After the incoming gas bubbles successively coalesce and increase in size at the SLIPS wall (bubble 1+2+3), the F _driven in Equation (1) above increases as V expands. As a result, when F _driven becomes greater than the underwater bubble motion resistance (F _resistance ), the gas bubble starts to move, which is the sum of the _{contact angle hysteresis (F CAH} ) and the drag resistance (F _{drag ).}

In the above equations (2) or (3), respectively, γ is the surface tension of the medium, L is the characteristic length of the gas bubble, and θa and θr are the forward and backward angles of the bubble, respectively. C _D is the drag coefficient of the water, v is the transport speed, S is the cross-sectional area of the gas bubble, and a and k are the undefined parameters for the resistive force developed in the lubricant layer, respectively.

After the gas bubble reaches the top edge of the electrode _{, it separates from the surface when the F driven} becomes greater than the adhesion of the SLIPS gas wall. In this way, the SLIPS gas wall suppresses lateral leakage of gas bubbles and improves gas collection efficiency.

To further validate the gas bubble manipulation ability of the SLIPS gas wall, the electrode was tilted at 30° and 30° to enhance gas leakage through the lateral edge of the electrode in the unmodified conventional electrode, as shown in Fig. 3b. tilted horizontally to Under these conditions, rapid gas leakage is clearly observed at the side edge of the exposed Ni-Pt electrode (Fig. S3) due to the absence of a barrier wall. On the other hand, gas bubbles moving to the side of the electrode (Fig. 3b(i)) are tightly trapped in the SLIPS-modified sidewall (Fig. 3b(ii)). As the size increases, gas bubbles are carried along the SLIPS wall to the top edge of the electrode without leakage (Fig. 3b(iii)). At the top edge, gas bubbles are easily separated from the electrode surface for collection (Fig. 3b(iv)).

The unique SLIPS edge design of the present invention was applied to both the HER and OER electrodes of the entire water electrolysis system. The inclined HER and OER electrodes were combined as shown in FIG. 3c to have a compact arrangement for selective H ₂ /O _{2 gas collection.} Pt/Ni and Ni(Fe)O/Ni thin films were prepared with HER and OER catalysts, respectively, using sputtering and precursor solution coating methods. For the water electrolysis reaction, an electrical bias was applied between the two electrodes to generate an 8 mA current in 0.1 M KOH electrolyte, and then the resulting gas was analyzed by gas chromatography (GC). _{3D depicts H 2} gas product collection yields with various operating times for various electrode arrangements for comparison. Three arrays were compared; i) planar, with bare electrodes (PBE), ii) inclined, with bare electrodes (IBE), and iii) inclined, with SLIPS-edged electrodes (ISE) . When the generated photocharge (Q) is completely used for water electrolysis, the gas production of an ideal molar amount (n) can be calculated as in Equation (4) below through the ideal Faraday's law.

nFz = Q (4)

The F and z represent the Faraday constant and the number of electrons involved in the reaction, respectively.

Since _{the theoretical amount of H 2} gas collection was calculated to be 37.3 μmol during 15 min of electrolysis, ISE showed the highest H ₂ capture efficiency of 93.4% (34.8 μmol), demonstrating that the fuel gas collection was successful. For IBE, the efficiency of 48.8% (18.2 μmol) is much lower due to the lack of a SLIPS gas wall function in buoyant propulsion gas transport. The performance of PBEs recording efficiencies of less than 1% was worse because there is no _{F driven} of gas transport applied along the planar electrode arrangement direction with α value of 0°. These results clearly show the effect of ISE on gas capture/transport/collection in water electrolysis system. In _{addition to the H 2} collection efficiency, the purity of the fuel gas collection in the ISE was tested by measuring the _{H 2} and O ₂ gas composition at the HER/OER collection port using a GC every 5 min and the results of the purity ratio are shown in Figure 3e. H ₂ purity results recorded are 94.8, 96.5 and 96.1% at the HER collection port. At the opposite OER collection port, the H ₂ gas composition remains lower than 0.8% (0.14 μmol) during 15 min of electrolysis. This result demonstrates the effectiveness of the gas separation system in preventing crossover of the _{generated H 2} /O ₂ gas bubbles and obtaining a very pure product, even at low current scales where small amounts of impurities can be fatal.

Experimental Example 4. Analysis of Optimal Efficiency of Membrane-Free Artificial Leaf Device

Equipping a monolithic PV electrolysis system with ISE enables the implementation of an ideal miniature artificial leaf device with membrane-less gas separation/collection capabilities. To induce a water separation reaction, a series-type thin-film CIS PV cell was applied to generate a photovoltage. As shown in Fig. 4a, superstrate CIS/CdS/ZnO nanorod (NR) thin film PV cells were fabricated via a non-vacuum deposition process and interconnected to make a tandem PV cell configuration. The 1D nanostructured n-type CdS/ZnO NRs provide a large p-n junction with the p-type CIS absorption layer, aid in charge carrier separation/transport, and enhance light absorption through diffuse light scattering/reflection. These characteristics of the nanostructured CIS PV cell are shown in Fig. 4a. Another important advantage of tandem PV cells is that they easily control the photovoltage generation, as shown in FIG.

The combination of tandem CIS PV cells and ISE-modified HER/OER electrodes completes the monolithic artificial leaf system as shown in Fig. 4b. The interconnected PV cell layers were tightly sealed and encapsulated with biomimetic modified electrodes and polymer films to protect the units from contact with aqueous solutions. Due to their unique capsule design, these monolithic modules can float on the water surface, allowing maximum utilization and reuse of solar lighting (Fig. 4c). The optimal photocurrent generation of the PV electrolysis device is determined to be a 5.39% solar energy conversion efficiency in the two catalyzed electrode sets in the current density-voltage (JV) curves of the three interconnected PV cells. JV curves were recorded by linear sweeping between 0 and 3V under AM 1.5 illumination (100 mW/cm ^{2 ) in 1.0M KOH solution.} The intersection of the two JV curves represents the expected driving points of PV-electrolysis (3.37 mA/cm ² and 1.58 V) as shown in Fig. 4d. The measured photocurrent values from the actual PV-electrolysis in the wired arrangement are in good agreement and averaged 3.36 mA/cm ² . After preparing the monolithic artificial leaves, the product gas of solar water separation (H ₂ /O ₂ ) was collected and analyzed at each HER/OER gas collection port. As shown in Fig. 4c, the resulting gas bubbles were efficiently collected and transported onto the ISE-modified electrode surface. 4E shows stable gas product collection of _{H 2} /O ₂ during AM 1.5 illumination over 30 min of consistent photocurrent generation. Assuming that the Faraday efficiency is ideally 100% (ε = 1), the H ₂ collection yield is estimated to be approximately 93.2% (22.08 μmol) for 30 min of solar water separation, and the corresponding STH efficiency is calculated from the GC results and equation ( 5) was calculated using

where P _in is the power density of the incident light, 100 mW/cm ² , G ° _f is the Gibbs free energy for generating _{H 2} by water electrolysis (237.15 KJ/H ₂ mol) , and n (H ₂ ) is the collection is the molar amount of H _{2 gas.} t is the illumination time and A is the active area of ^{0.75 cm 2 measured in series from the PV cell.} J _working is the driving current density during PV-electrolysis, which is 3.37 mA/cm ² .

The corresponding O ₂ gas collection represents the stoichiometric proportion of the water separation reaction, which is approximately half (10.53 μmol) of the _{H 2 collection, confirming the actual solar water separation.} The crossover of the gas is effectively limited as recorded very little H ₂ (0.17%), and most of the H ₂ gas is collected at the HER collection port as shown in FIG. 4E . These results clearly show that the biomimetic surface design ISE of the present invention is very efficient for developing a membrane-free monolithic artificial leaf system for product gas separation and collection.

The present inventors have invented a set of HER/OER electrodes that are biomimetic and surface modified in an inclined arrangement to efficiently separate, transport and collect gaseous products from water electrolysis that do not require conventional membrane systems. The SLIPS gas wall-modified HER/OER electrode of the present invention showed excellent selective gas collection efficiency in a monolithic artificial leaf device. Due to the proper aerobicity of the electrode and the adhesion value of gas bubbles, the SLIPS gas wall electrode has a shut-off leakage function, which safely traps, transports and collects the generated gas bubbles. As a result, _{the collection efficiency of H 2} gas at the HER port was recorded with high purity >90%, up to 95%, and the O ₂ gas collection, which is the opposite part of water electrolysis, has a very low crossover of _{less than 1% H 2 at the OER port.} showed high purity.

10: battery unit
11: light-transmitting substrate
12: transparent electrode
13: light absorption layer
131: nanostructure core
132: nanoshell
133: infiltration layer
14: back electrode
20: electrode part

Claims (11)

As an artificial leaf device that can be operated by floating on water,
a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of water by using light energy; and
a hydrogen generating electrode unit receiving electric potential from the battery unit to decompose water through electrolysis and an electrode unit generating oxygen gas; including,
At the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,
The electrode part has a slippery liquid infused porous surface to collect hydrogen gas or oxygen gas generated from water electrolysis,
The deposition layer constituting the battery unit is provided to face inside the triangular structure,
A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the water,
artificial leaf device. The artificial leaf device according to claim 1, wherein the cell unit is a series-type solar cell in which at least two or more superstrate-type solar cell unit units are connected. According to claim 2, wherein the battery unit is a CIS-based solar cells are connected in series,
The artificial leaf device, characterized in that the CIS layer of the CIS-based solar cell is located at the top of the cell unit and is exposed on the water when the artificial leaf device is floated on the water. The artificial leaf device according to claim 1, wherein the two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other and are present in water when the artificial leaf device is floated on water. The method according to claim 1, wherein the hydrogen generating electrode part comprises a hydrogen generating catalyst layer having a thickness of 2 to 3 nm,
The hydrogen generation catalyst layer may include at least one noble metal selected from platinum (Pt), gold (Au), rhodium (Rh), and iridium (Ir); at least one compound selected from CoS, MoS and CoP; or Ni, Mo, Co, Cu, and an artificial leaf device comprising at least one alloy selected from Fe. According to claim 1, wherein the electrode for generating the oxygen gas comprises an oxygen generation catalyst layer of 30 to 40nm thickness,
The oxygen evolution catalyst layer may include at least one noble metal oxide selected from RuO and IrO; at least one oxide selected from NiO, Co ₃ O ₄ , and MnO _{2 ;} or (Ni,Fe)O-doped oxide comprising an artificial leaf device. The method of claim 1 . In the triangle, the angle formed by the battery unit and the hydrogen generating electrode unit is the same as the angle formed by the battery unit and the electrode unit generating oxygen gas, and the triangle is an isosceles triangle. The method of claim 7, wherein in the triangle, the angle formed by the battery unit and the hydrogen generating electrode unit and the angle formed by the battery unit and the electrode unit generating oxygen gas are each 30°, and the direction of the side of the electrode unit forming the triangle is An artificial leaf device with a length of 2.6 cm. A method for collecting hydrogen gas using the artificial leaf device according to any one of claims 1 to 8. The method of collecting oxygen gas using the artificial leaf device according to any one of claims 1 to 8. As an artificial leaf device that can be operated by floating on a liquid,
a battery unit including a deposition layer configured to provide a potential necessary for electrolysis of a liquid by using light energy; and
an oxidation electrode unit and a reduction electrode unit receiving a potential from the battery unit and decomposing the liquid through electrolysis; including,
At the bottom of the battery part, two electrode parts are connected to both ends of the battery part, and the two electrode parts are connected to each other, so that the two electrode parts and the battery part form a triangular structure,
The electrode part has a slippery liquid infused porous surface so as to collect the gas generated from the electrolysis of the liquid,
The deposition layer constituting the battery unit is provided to face inside the triangular structure,
A slippery liquid infused porous surface on the electrode part is provided to face out of the triangular structure and is in contact with the liquid,
artificial leaf device.

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