Electrode for alkaline hydrogen evolution reaction comprising nafion and metal-organic framework composite and manufacturing method thereof

Abstract

The present invention relates to an electrode for a hydrogen evolution reaction of an alkaline water electrolysis cell, the electrode being characterized by comprising: a cocatalyst which is a composite comprising a Lewis acid-containing material and a metal-organic framework (MOF); and a catalyst surrounded by the cocatalyst. Therefore, according to the present invention, a water dissociation step of an alkaline hydrogen evolution reaction is promoted, hydrogen gas generated by the hydrogen evolution reaction is easily permeated, and Nafion is evenly dispersed by large pores generated by the MOF, thereby minimizing catalyst poisoning while implementing the effect of the cocatalyst on the entire surface.

Description

Electrode for alkaline hydrogen evolution reaction comprising Nafion and metal-organic framework complex and method for manufacturing the same

[0001] The present invention relates to an electrode for an alkaline hydrogen generation reaction and a method for manufacturing the same, and more particularly, to an electrode for an alkaline hydrogen generation reaction that is highly effective in water activation by a catalyst comprising a Nafion and a metal organic framework (MOF) complex and a method for manufacturing the same.

[0002] Hydrogen does not exist independently in nature; it mostly exists as a compound, combined with other elements. Therefore, to be used as an energy source, it must undergo a separate production process. The most common methods for producing hydrogen include "byproduct hydrogen," which is generated as a byproduct during processes like petrochemicals or steelmaking; "reformed hydrogen," which is produced by decomposing natural gas at high temperatures and pressures; and "water electrolysis," which uses water electrolysis to produce hydrogen. Water electrolysis is environmentally friendly, emitting no carbon dioxide during the hydrogen extraction process, and is attracting attention as the ultimate technology to pursue in the era of carbon neutrality.

[0003] Among these, alkaline electrolysis (AEC) uses an alkaline electrolyte to electrolyze water. It is the most commercialized technology among electrolysis methods and boasts the advantage of stability, thanks to its long history of research. Recently, research is being conducted on electrolysis technologies that utilize metal oxides, chalcogens, or halogen elements as cocatalysts to accelerate the water dissociation step of the alkaline hydrogen evolution reaction, thereby reducing activation loss.

[0004] However, metal oxide and chalcogen / halogen element-based promoters for inducing water dissociation have limitations: their activity is maximized only on the catalyst surface adjacent to the promoter, and they partially poison the catalyst surface where the reaction can occur. This necessitates a new paradigm in catalyst design to minimize activation loss in the alkaline water dissociation step. Furthermore, utilizing metal oxide, chalcogen, and halogen element-based promoters requires the hassle of finding new synthesis methods and compositions tailored to the type of catalyst used.

[0005] The problem to be solved by the present invention is to provide an electrode for alkaline hydrogen generation reaction comprising a composite of Nafion and MOF to efficiently promote the water dissociation step of the alkaline hydrogen generation reaction.

[0006] In particular, the present invention provides an electrode for an alkaline hydrogen evolution reaction that can easily transmit hydrogen gas generated by a hydrogen evolution reaction using MOF together with Nafion, and can evenly disperse Nafion through large pores generated by MOF, thereby implementing the effect of a co-catalyst over the entire surface while minimizing catalyst poisoning.

[0007] The tasks of the present invention are not limited to the tasks mentioned above, and other tasks not mentioned will be clearly understood by those skilled in the art of the present invention from the description below.

[0008] In order to solve the aforementioned problem, an electrode for hydrogen generation reaction of an alkaline water electrolysis cell according to one embodiment of the present invention may include a cocatalyst which is a complex including a material including a Lewis acid and a metal-organic framework (MOF); and a catalyst surrounded by the cocatalyst.

[0009] In this case, the material containing the Lewis acid may include Nafion.

[0010] Meanwhile, the metal-organic framework may have a pore size of 6 Å or more.

[0011] In addition, the metal-organic framework may be selected from the group consisting of Zr-UiO-66, Ti-MIL-125, Zn-ZIF-69, Zr-UiO-66 octahedral, Zn-ZIF-78, Zn-ZIF-79, Zn-ZIF-81, AL-MIL-53-NH3, Zr-UiO-68, Zn-MOF-74, Zn-ZIF-68, Zn-ZIF-80, Zr-UiO-67, Zn-ZIF-80, Zn-ZIF-82, Al-MIL-53, Zn-ZIF-70, Cu-MOF-74, and Cr-MIL-101.

[0012] Additionally, the mass ratio of the catalyst and the metal-organic framework may be 1:10 or less.

[0013] In addition, the catalyst may be at least one selected from the group consisting of Pt / C, nickel nanopowder, NiMo / C, Ni-based catalysts, Cu-based catalysts, and Co-based catalysts.

[0014] Meanwhile, according to an embodiment of the present invention, in an alkaline water electrolysis cell including an end plate, a collector plate, an anode, a cathode, a porous transport layer, and a separator, the cathode may include a cocatalyst which is a complex including a material including a Lewis acid and a metal-organic framework (MOF); and a catalyst surrounded by the cocatalyst.

[0015] Specific details of other embodiments are included in the detailed description and drawings.

[0016] In the case of the Nafion / Cr-Mil-101 ​​co-catalyst combination according to the embodiment of the present invention, 10 mA / cm of Pt / C catalyst 2The effect of significantly reducing the overvoltage in the alkaline environment was confirmed (96 mV->45 mV). This can be expected to significantly improve the performance of the hydrogen generation reaction catalyst in an alkaline environment that shows activation loss compared to an acidic environment, thereby accelerating the commercialization of water electrolysis technology in an alkaline environment.

[0017] In addition, according to the present invention, it was confirmed that the performance of the hydrogen evolution reaction in an alkaline water electrolysis cell can be improved when loading a MOF material other than Cr-Mil-101, and it is significant that the co-catalyst combination was confirmed to work not only with a Pt / C catalyst but also with other hydrogen evolution reaction catalysts, thereby developing an electrode manufacturing method that can be commonly utilized in manufacturing a hydrogen evolution reaction electrode.

[0018] Therefore, according to the present invention, an electrode for alkaline hydrogen evolution reaction comprising a composite of Nafion and MOF can be provided to efficiently promote the water dissociation step of the alkaline hydrogen evolution reaction.

[0019] In addition, the present invention can provide an electrode for an alkaline hydrogen generation reaction that can easily transmit hydrogen gas generated by a hydrogen generation reaction and evenly disperse Nafion through large pores generated by MOF, thereby implementing the effect of a co-catalyst over the entire surface while minimizing catalyst poisoning.

[0020] The effects according to the present invention are not limited to those exemplified above, and other effects can be clearly understood by those skilled in the art from the description of the following specification.

[0021] Figure 1 is a schematic diagram of an electrode for hydrogen generation reaction and a reaction at the electrode according to an embodiment of the present invention.

[0022] Figure 2 is a drawing showing the pore size of MOF.

[0023] FIG. 3 is a graph of voltage and current density when a nickel nanopowder catalyst and a cocatalyst including MOF are used according to an embodiment of the present invention.

[0024] Figure 4 is a graph showing performance improvement according to changes in the ratio of catalyst and MOF according to an embodiment of the present invention.

[0025] FIG. 5 is a graph showing performance improvement according to MOF material according to an embodiment of the present invention.

[0026] Figure 6 is a graph showing performance improvement according to changes in the ratio of NiMo / C catalyst and MOF according to an embodiment of the present invention.

[0027] FIG. 7 is a diagram illustrating an exemplary alkaline water electrolysis cell (AEMWE) according to an embodiment of the present invention.

[0028] Figure 8 is a graph showing performance improvement in an actual water electrolysis cell according to an embodiment of the present invention.

[0029] FIG. 9 is a diagram showing the performance improvement when nickel nanopowder is used as a catalyst and a cocatalyst including MOF is used in an actual water electrolysis cell according to an embodiment of the present invention.

[0030] FIG. 10 is a diagram showing performance improvement according to the ratio of catalyst and MOF in an actual water electrolysis cell according to an embodiment of the present invention.

[0031] FIG. 11 is a diagram showing performance improvement according to changes in the ratio of Nafion in an actual water electrolysis cell according to an embodiment of the present invention.

[0032] Figure 12 is a schematic diagram of an electrode for hydrogen generation reaction according to a conventional technology and a reaction at the electrode.

[0033] Hereinafter, embodiments of the present application will be described in more detail with reference to the attached drawings. However, the technology disclosed in this application is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present application to those skilled in the art. That is, in order to clearly represent the components of each device in the drawings, the dimensions of the components, such as the width or thickness, may be slightly enlarged or reduced.

[0034] Additionally, for convenience of explanation, only some of the components are illustrated; however, those skilled in the art will readily understand the remaining components. Overall, the drawings are described from the observer's perspective, and when an element is referred to as being positioned above or below another element, this includes the implication that the element is positioned directly above or below the other element, or that additional elements may be interposed between the elements.

[0035] Furthermore, those skilled in the art will be able to implement the concepts of this application in various other forms without departing from the technical spirit of this application. Furthermore, identical reference numerals in multiple drawings indicate substantially identical elements.

[0036] In addition, singular expressions should be understood to include plural expressions unless the context clearly indicates otherwise, and terms such as include or have should be understood to specify the presence of the described feature, number, step, operation, component, part or combination thereof, but not to exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0037] Additionally, in performing a method or manufacturing method, each step constituting the method may occur in a different order than the stated order, unless the context clearly indicates a specific order. That is, each step may occur in the same order as the stated order, may be performed substantially simultaneously, or may be performed in the opposite order.

[0038] Hereinafter, various embodiments of the present invention will be described in detail with reference to the attached drawings.

[0039] First, the limitations of the prior art will be examined with reference to Fig. 12. Fig. 12 is a schematic diagram of a hydrogen generation reaction of an alkaline water electrolysis cell according to the prior art. According to Fig. 11, the electrode for the hydrogen generation reaction includes a co-catalyst (210) and a catalyst (220). In this case, the co-catalyst (210) includes a metal oxide and a chalcogen or halogen element and is used to induce water dissociation. In this case, there is a problem that the catalyst (220) region (230) not adjacent to the co-catalyst (210) is not affected by the co-catalyst, thereby reducing the occurrence of the reaction. In addition, although the activity is maximized in the region (240) of the catalyst surface adjacent to the co-catalyst, there is a limitation that the surface of the catalyst where the reaction can occur is partially poisoned.

[0040] Referring to Fig. 1, the electrode (200) for hydrogen generation reaction of the alkaline water electrolysis cell according to the present invention to solve such problems may include a co-catalyst (210) and a catalyst (220). At this time, the co-catalyst (210) may include a composite including a material (250) containing a Lewis acid and a metal organic framework (MOF, Metal Organic Framework, 260). Preferably, the catalyst material, the material containing a Lewis acid, and the metal organic framework powder are mixed and manufactured, so that all materials are evenly dispersed on the surface, thereby maximizing the effects of the catalyst and co-catalyst.

[0041] In this case, the material (250) containing the Lewis acid of the cocatalyst (210) can utilize, for example, Nafion, and the embodiment was described with a focus on utilizing Nafion. However, the cocatalyst (210) is SO3H of Nafion. - It utilizes the property that a portion acts as a Lewis acid and has a hydrophilic tendency, and HCl, HNO3, carboxylic acid, phenol, alcohol, Li, etc., which play the same role. + , Mg 2+ , materials containing Lewis acid moieties such as AlCl3 can be utilized.

[0042] MOF (260) is a porous material in which metal ions, etc. are connected by organic ligands, and is a type of coordination polymer. When a complex of a material (250) containing a Lewis acid and MOF (260) is utilized as a cocatalyst (210), the material (250) containing a Lewis acid is evenly dispersed over the entire catalyst surface by MOF (260), and hydrogen gas can easily permeate through the pores of MOF (260), thereby minimizing catalyst poisoning. In this case, it is preferable to use a MIL-based or UiO-based MOF, and furthermore, it is preferable to use a Cr-based or Zr-based MOF.

[0043] In one embodiment of the present invention, Cr-MIL-101 was utilized as MOF (260), but as a result of the experiment, it was experimentally confirmed that MOF (250) can promote water dissociation by maximizing the interaction between the catalyst surface that causes the hydrogen evolution reaction and the hydrated cation in the case of a group of MOF materials having a pore size of 6 Å or more, as in the present invention. Referring to Fig. 2, a group of MOF materials having a pore size of 6 Å or more is exemplified. For example, MOF (250) is Zr-UiO-66, Ti-MIL-125, Zn-ZIF-69, Zr-UiO-66 octahedral, Zn-ZIF-78, Zn-ZIF-79, Zn-ZIF-81, AL-MIL-53-NH3, Zr-UiO-68, Zn-MOF-74, It may be Zn-ZIF-68, Zn-ZIF-80, Zr-UiO-67, Zn-ZIF-80, Zn-ZIF-82, Al-MIL-53, Zn-ZIF-70, Cu-MOF-74 or Cr-MIL-101.

[0044] The catalyst (220) can be typically Pt / C, but in addition, for example, nickel nanopowder, NiMo / C, Ni-based catalysts (Ni, Ni compounds and Ni-based alloy catalysts) used as electrolysis catalysts, Cu-based catalysts (Cu-based alloy catalysts including Cu, Cu compounds), Co-based catalysts (Co-based alloy or Spinel structure catalysts), 3d transition metal catalysts and 3d transition metal-based alloy catalysts, and Pt, Ir catalysts and Pt, Ir-based alloy catalysts can be used. Referring to FIG. 3, it shows that there is an effect of improving catalytic performance even when nickel nanopowder and NiMo / C are used as catalysts and Cr-MIL-101 is used as MOF.

[0045] Method for manufacturing an electrode for hydrogen generation reaction

[0046] Hereinafter, with reference to FIGS. 4 to 8, a method for manufacturing an electrode for hydrogen generation reaction of an alkaline water electrolysis cell according to an embodiment of the present invention will be described in detail.

[0047] In an embodiment of the present invention, a composite of Nafion, a material (250) containing Lewis acid, and MOF (260) was used as a cocatalyst (210) to manufacture an electrode for promoting the water dissociation step of the alkaline hydrogen evolution reaction. In the case of Nafion, an ion transport polymer, SO3H for cation transport - It has an ion-affinity region like a zirconia. Therefore, Nafion is a hydrated cation (C) in the electrolyte. + -(H2O) x ) and van der Waals attraction, which can play a role in pulling hydrated cations close to the catalyst. This maximizes the interaction between the catalyst surface and hydrated cations that cause the hydrogen evolution reaction, thereby promoting water dissociation.

[0048] In addition, in the embodiment of the present invention, hydrogen gas generated through a hydrogen evolution reaction through the pores of MOF (260) together with Nafion can be easily permeated, and Nafion can be evenly dispersed, thereby implementing the effect of a co-catalyst over the entire surface while minimizing catalyst poisoning.

[0049] According to an embodiment of the present invention, in order to find the optimal cocatalyst composition, a Pt / C catalyst was used as a hydrogen generation reaction catalyst, and the loading amount of Pt was 20 ug / cm 2 , the loading amount of Nafion is 10ug / cm 2 The loading amount of Cr-Mil-101, which is a MOF, was adjusted and composition screening was performed.

[0050]

[0051] For this purpose, the electrode manufacturing method is as follows.

[0052] a. Stir the Nafion solution (DI water: 80 mL / IPA (Isopropyl Alcohol): 20 mL / 5 wt% Nafion: 2 mL) at room temperature for 24 hours.

[0053] b. Disperse the Nafion solution using a tip sonicator according to the ratio of Pt / C and Cr-Mil-101 ​​(1 hour).

[0054] c. 10 μL of Nafion solution with Pt / C and Cr-Mil-101 ​​dispersed was placed on GC (glassy carbon) and dried overnight.

[0055]

[0056] The evaluation method and criteria for the electrodes manufactured using the above method are as follows.

[0057] A three-electrode cell for RDE experiments was constructed using the fabricated catalyst, and the HER polarization curve was measured under room temperature and pressure conditions. From the obtained polarization curve, a constant current density (10 mA / cm 2 ) to read the potential.

[0058] - Overall experimental conditions

[0059] a. Working electrode - RDE (Rotating Disk Electrode)

[0060] Reference electrode - Hg / HgOl

[0061] Counter electrode - Pt Wire

[0062] b. Electrolyte: 0.1 M KOH (pH 13)

[0063] c. Temperature: Room temperature (25℃)

[0064] - HER activity evaluation experiment

[0065] a. Purging the electrolyte with hydrogen for 30 minutes

[0066] b. Rotate the working electrode at 1600 rpm to remove hydrogen gas from the HER.

[0067] c. Scan rate: 10mV / s

[0068] d. Scan range: 0.1 V (vs RHE) ~ -0.5 V (vs RHE)

[0069]

[0070] SamplePt : 20ugPt : 20ug / cm2Cr-Mil-101 ​​: 50ug / cm2Pt : 20ug / cm2Cr-Mil-101 ​​: 100ug / cm2Pt : 20ug / cm2Cr-Mil-101 ​​: 150ug / cm2Pt : 20ug / cm2Cr-Mil-101 ​​: 200ug / cm2Pt : 20ug / cm2Cr-Mil-101 ​​: 300ug / cm2η(mV, @10 mA cm -2 )9689456098195

[0071] Referring to Fig. 4 and Table 1, when MOF Cr-Mil-101 ​​is loaded, the overvoltage begins to gradually decrease and continues to decrease until the ratio of Pt to Cr-Mil-101 ​​becomes 1:5. When the ratio of Pt to Cr-Mil-101 ​​is 1:5, the overvoltage is 45 mV, which is significantly lower than the overvoltage (96 mV) of the control group Pt / C. However, the overvoltage begins to increase again thereafter, and when the ratio of Pt to Cr-Mil-101 ​​is 1:10, the overvoltage is almost the same as before loading Cr-Mil-101, and it can be confirmed that the overvoltage increases as the ratio of Cr-Mil-101 ​​increases further. That is, in this experiment, it can be confirmed that there is a significant increase in the performance of overvoltage reduction when the loading amount of Pt:MOF is 1:10 or less.

[0072]

[0073] Meanwhile, in order to confirm the promotion effect of the hydrogen generation reaction according to the composition of Cr-MiL-101 and Nafion co-catalyst, 1) the effect of other MOFs other than Cr-Mil-101 ​​was confirmed, and 2) the effect of other catalysts other than Pt / C catalyst was confirmed.

[0074]

[0075] 1) Confirmation of the hydrogen generation reaction promotion effect in different types of MOF combinations

[0076] Referring to Fig. 5, electrodes were fabricated by applying the previously confirmed Pt:MOF 1:5 ratio condition to representative MOFs other than Cr-Mil-101, UIO-66 and ZIF-8 (same as the Cr-Mil-101-based electrode fabrication method described above). As a result of evaluating the hydrogen evolution reaction through this, it was confirmed that other MOFs other than Cr-Mil-101 ​​did not show a significant difference from the control group, Pt / C. This allows us to know that the effect occurs characteristically for Cr-Mil-101. In this case, the pore size of the MOF is important, and referring to Figs. 2 and 5 together, it was confirmed that the hydrogen evolution reaction promotion effect appeared in MOF materials with pores of approximately 6 Å or more.

[0077]

[0078] 2) Confirmation of the effectiveness of the above co-catalyst combination on other hydrogen evolution reaction catalysts (non-precious metal catalysts) other than Pt / C.

[0079] Meanwhile, referring to Fig. 6, the effect of the Cr-Mil-101 / Nafion promoter combination was confirmed for the NiMo / C catalyst, which is a representative non-precious metal hydrogen evolution reaction catalyst. To this end, the electrode was manufactured using the NiMo / C catalyst, while fixing the loading amount of the NiMo / C catalyst to 250 μg / cm², and adjusting the Cr-Mil-101 ​​ratios to 0, 50, and 100 μg / cm², respectively (the electrode manufacturing method other than the loading amount is the same as the method described above, and in the case of the non-precious metal catalyst, a higher loading amount than the precious metal catalyst can be used). As a result of evaluating the hydrogen evolution reaction using the manufactured electrode, it was confirmed that improved performance was shown when the loading amount of Cr-Mil-101 ​​was 100 μg / cm².

[0080]

[0081] Alkaline electrolysis cell

[0082] Hereinafter, the stack structure of an AEMWE cell according to an embodiment of the present invention will be described with reference to FIG. 7. FIG. 1 is a drawing showing an alkaline water electrolysis cell including an electrode according to an embodiment of the present invention.

[0083] Referring to FIG. 7, an AEC cell (100) according to one embodiment of the present invention may include an end plate (110), a current collector (120), a positive electrode (130), a porous transport layer (PTL, 140), an anode (150), a cathode (160), and a separator (170). In this case, as in the present embodiment, a stack of AWE cells (100) may be assembled with two zero gap type single cells, but this is merely an exemplary embodiment, and two or more single cells may be stacked and assembled.

[0084] The end plate (110) enables each component to be uniformly compressed and fastened by bolts / nuts when assembling the AEC cell (100), and can protect the positive electrode plate (130), porous transport layer (140), anode (150), cathode (160), and separator when fastened and fastened.

[0085] The collector plate (120) is connected to a power source and can supply the current (electrons) required for electrolysis to the entire system.

[0086] The bipolar plate (130) has a fluid path formed inside, through which electrolyte is supplied, and nitrogen generated through an oxidation reaction at the cathode and hydrogen generated through a reduction reaction at the anode are discharged. The bipolar plate (130) can be manufactured, for example, using commercial Ni foam. The bipolar plate is connected to a manifold (not shown) and receives the required electrolyte through the manifold.

[0087] The porous transport layer (PTL, 140) is located outside the electrode and can evenly distribute the electrolyte supplied from the separator to the electrode surface and discharge bubble gas generated on the electrode surface to the outside. For example, it can be made of nickel foam (Ni Foam).

[0088] The anode (150) and cathode (160) can form a cell voltage through a redox reaction. In this case, the anode (150) can be made of, for example, nickel foam, and the method for manufacturing the cathode (160) corresponding to one embodiment of the present invention has been described above.

[0089] The separator (170) is an electrical insulator and hydroxide (OH) is produced during hydrogen production. -) acts as a medium for transferring ions and simultaneously performs the role of physically separating oxygen and hydrogen. The separator material must be durable in a strong alkaline environment (30% KOH) exceeding 80°C and have low gas permeability to prevent hydrogen and oxygen gases generated at both electrodes from mixing. At the same time, high ion conductivity is required. The separator (140) can be made of, for example, zirfon.

[0090]

[0091] FIGS. 8 to 11 are graphs showing the results of evaluating a water electrolysis cell according to an embodiment of the present invention in an actual water electrolysis cell. Referring to FIG. 8, it can be seen that when materials of Nafion and MOF (Cr-Mil-101) are used as co-catalysts of the cathode (160) in an actual water electrolysis cell, the current density increases at the same cell voltage, thereby increasing performance. Meanwhile, referring to FIG. 9, it can be seen that even when nickel nanopowder, which is an alternative catalyst, is used, when materials of Nafion and MOF (Cr-Mil-101) are used as co-catalysts, the current density increases at the same cell voltage, thereby increasing performance.

[0092] Figure 10 is a graph showing performance according to MOF material in an actual cell. In this case, it was found that performance increased the most when the Pt:MOF loading was 1:1 in an actual cell. While the optimal Pt:MOF ratio may vary depending on the system, it was confirmed that performance increased when MOF was used as a cocatalyst, but decreased when the amount exceeded a certain level.

[0093] Fig. 11 is a graph showing the performance according to the amount of Nafion when implementing an electrode according to an embodiment of the present invention in an actual cell. In this case, I represents Nafion, which is an ionomer, and C represents carbon, and this graph shows the change in performance according to the ratio of Nafion in the electrode. In this case, it can be seen that the most optimal performance is shown when the I / C is 0.6. In other words, it was confirmed that when a composite of Nafion and MOF material is used as a cocatalyst, the performance increases until the ratio of Nafion reaches a certain value, but when the ratio of Nafion exceeds a certain value, the performance decreases again.

[0094] Therefore, according to the present invention, in the case of the Nafion / Cr-Mil-101 ​​cocatalyst combination, the effect of significantly reducing the overvoltage in the Pt / C catalyst was confirmed, and this can be expected to significantly improve the hydrogen generation reaction catalytic performance in an alkaline environment that shows activation loss compared to an acidic environment, thereby accelerating the commercialization of water electrolysis technology in an alkaline environment.

[0095] In addition, according to the present invention, it was confirmed that the performance of the hydrogen generation reaction in an alkaline water electrolysis cell can be improved when loading a MOF material other than Cr-Mil-101, and it was confirmed that the co-catalyst combination works not only with a Pt / C catalyst but also with other hydrogen generation reaction catalysts, so that an electrode manufacturing method that can be commonly utilized in manufacturing a hydrogen generation reaction electrode can be provided.

[0096] Therefore, according to the present invention, an electrode for alkaline hydrogen evolution reaction comprising a composite of Nafion and MOF can be provided to efficiently promote the water dissociation step of the alkaline hydrogen evolution reaction.

[0097] In addition, the present invention can provide an electrode for an alkaline hydrogen generation reaction that can easily transmit hydrogen gas generated by a hydrogen generation reaction and evenly disperse Nafion through large pores generated by MOF, thereby implementing the effect of a co-catalyst over the entire surface while minimizing catalyst poisoning.

[0098] Although the embodiments of the present invention have been described in more detail with reference to the attached drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be implemented without departing from the technical spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain it, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive. The protection scope of the present invention should be interpreted by the claims below, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. In the electrode for hydrogen generation reaction of an alkaline water electrolysis cell, The electrode comprises a cocatalyst which is a complex comprising a material including a Lewis acid and a metal-organic framework (MOF); and An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that it comprises a catalyst surrounded by the above-mentioned cocatalyst.

2. In paragraph 1, The substances containing the above Lewis acid are Nafion, HCl, HNO3, carboxylic acid, phenol, alcohol, Li + , Mg 2+ An electrode for hydrogen generation reaction of an alkaline water electrolysis cell characterized by containing any one of AlCl3.

3. In paragraph 1, An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that the metal-organic framework has a pore size of 6 Å or more.

4. In paragraph 3, An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that the metal-organic framework is selected from the group consisting of Zr-UiO-66, Ti-MIL-125, Zn-ZIF-69, Zr-UiO-66 octahedral, Zn-ZIF-78, Zn-ZIF-79, Zn-ZIF-81, AL-MIL-53-NH3, Zr-UiO-68, Zn-MOF-74, Zn-ZIF-68, Zn-ZIF-80, Zr-UiO-67, Zn-ZIF-80, Zn-ZIF-82, Al-MIL-53, Zn-ZIF-70, Cu-MOF-74, and Cr-MIL-101.

5. In paragraph 1, An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that the mass ratio of the catalyst and the metal-organic framework is 1:10 or less.

6. In paragraph 1, An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that the catalyst is at least one selected from the group consisting of Pt / C, nickel nanopowder, NiMo / C, Ni-based catalysts, Cu-based catalysts, and Co-based catalysts.

7. In an alkaline water electrolysis cell comprising an end plate, a collector plate, an anode, a cathode, a porous transport layer and a separator, The cathode comprises a cocatalyst which is a complex comprising a material including a Lewis acid and a metal-organic framework (MOF); and An alkaline water electrolysis cell characterized by comprising a catalyst surrounded by the above-mentioned cocatalyst.

8. In paragraph 7, The substances containing the above Lewis acid are Nafion, HCl, HNO3, carboxylic acid, phenol, alcohol, Li + , Mg 2+ , Alkaline water electrolysis cell characterized by containing any one of AlCl3.

9. In paragraph 7, An alkaline water electrolysis cell characterized in that the metal-organic framework has a pore size of 6 Å or more.

10. In paragraph 7, An alkaline water electrolysis cell characterized in that the metal-organic framework is selected from the group consisting of Zr-UiO-66, Ti-MIL-125, Zn-ZIF-69, Zr-UiO-66 octahedral, Zn-ZIF-78, Zn-ZIF-79, Zn-ZIF-81, AL-MIL-53-NH3, Zr-UiO-68, Zn-MOF-74, Zn-ZIF-68, Zn-ZIF-80, Zr-UiO-67, Zn-ZIF-80, Zn-ZIF-82, Al-MIL-53, Zn-ZIF-70, Cu-MOF-74, and Cr-MIL-101.

11. In paragraph 7, An alkaline water electrolysis cell characterized in that the mass ratio of the catalyst and the metal-organic framework is 1:10 or less.

12. In paragraph 7, An electrode for hydrogen generation reaction of an alkaline water electrolysis cell, characterized in that the catalyst is at least one selected from the group consisting of Pt / C, nickel nanopowder, NiMo / C, Ni-based catalysts, Cu-based catalysts, and Co-based catalysts.

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