CN116157202A - Electrode catalyst for water electrolysis cell, water electrolysis cell and water electrolysis device - Google Patents

Electrode catalyst for water electrolysis cell, water electrolysis cell and water electrolysis device Download PDF

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CN116157202A
CN116157202A CN202180061479.8A CN202180061479A CN116157202A CN 116157202 A CN116157202 A CN 116157202A CN 202180061479 A CN202180061479 A CN 202180061479A CN 116157202 A CN116157202 A CN 116157202A
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water electrolysis
electrolysis cell
catalyst
anode
electrode catalyst
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白泷浩志
林隆夫
村濑英昭
铃鹿理生
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Panasonic Intellectual Property Management Co Ltd
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

An electrode catalyst for a water electrolysis cell, comprising a catalyst and a neutral inherently microporous polymer.

Description

Electrode catalyst for water electrolysis cell, water electrolysis cell and water electrolysis device
Technical Field
The present disclosure relates to an electrode catalyst for a water electrolysis cell, and a water electrolysis apparatus.
Background
In recent years, development of a catalyst material usable for a water electrolysis apparatus has been desired.
Patent document 1 discloses a polymer having a tertagine skeleton. Patent document 2 discloses a polymer having a spirobiindane skeleton. Patent document 3 discloses a polymer film containing imide groups.
Non-patent document 1 discloses a film containing an inherently microporous polymer (Polymers of Intrinsic Microporosity, PIM). Non-patent document 2 discloses a porous polymer having tertagine.
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/091357
Patent document 2: international publication No. 2005/012397
Patent document 3: U.S. patent application publication No. 2014/255636 specification
Non-patent literature
Non-patent document 1: canghai Ma et al Polymers ofIntrinsic Microporosity (PIMs) Gas Separation Membranes: A mini Review (PIMs), proceedings ofthe Nature Research Society,2018, vol.2, no.02002, p.1-19
Non-patent document 2: mariolino Carta et al, the synthesis of microporous polymers using Troger's base information, polymer Chemistry,2014, vol.5, p.5267-5272
Disclosure of Invention
Problems to be solved by the invention
The present disclosure provides electrode catalysts with low overvoltage water electrolysis cells.
Means for solving the problems
One embodiment of the present disclosure provides an electrode catalyst for a water electrolysis cell, comprising:
catalyst and process for preparing the same
Neutral inherently microporous polymers.
Effects of the invention
According to the present disclosure, an electrode catalyst having a low overvoltage water electrolysis cell may be provided.
Drawings
Fig. 1 is a view schematically showing an electrode catalyst of a water electrolysis cell according to embodiment 1.
Fig. 2 is a diagram schematically showing an example of the crystal structure of a layered double hydride (layered double hydride, LDH).
Fig. 3 is a cross-sectional view schematically showing an example of the water electrolysis cell according to embodiment 2.
Fig. 4 is a cross-sectional view schematically showing an example of the water electrolysis apparatus according to embodiment 3.
Fig. 5 is a cross-sectional view schematically showing another example of the water electrolysis cell according to embodiment 4.
Fig. 6 is a cross-sectional view schematically showing another example of the water electrolysis apparatus according to embodiment 5.
Detailed Description
(insight underlying the present disclosure)
As a countermeasure against global warming, the use of renewable energy sources such as sunlight and wind power is attracting attention. However, in the power generation using renewable energy sources, surplus power is wasted. Therefore, the utilization efficiency of renewable energy is not necessarily sufficient. Therefore, a method of producing hydrogen using surplus electric power and storing the hydrogen has been studied.
As a method for producing hydrogen using surplus power, electrolysis of water is generally used. Electrolysis of water is also known as water electrolysis. In order to produce hydrogen stably at low cost, it is necessary to develop a water electrolysis apparatus having high efficiency and long life. As a main component of the water electrolysis apparatus, a Membrane Electrode Assembly (MEA) composed of a gas diffusion layer, a catalyst, and an electrolyte membrane is exemplified.
In order to provide a highly efficient and long-life water electrolysis apparatus, it is particularly necessary to improve the performance of the catalyst and the durability of the catalyst. In the electrode catalyst of the water electrolysis cell, an organic material may be used in order to improve the dispersibility of the catalyst material and/or to improve the bonding force to a substrate such as an electrode. By using an organic material, the dispersibility of the catalyst material or the binding force to the substrate can be improved.
However, typically, the organic material has a large electrical resistance, and when a voltage is applied, the organic material covers the active sites on the surface of the catalyst, and thus the overvoltage increases. Therefore, it is important to provide an electrode catalyst capable of reducing the loss due to the overvoltage of the electrode even in the case of using an organic material. Accordingly, the inventors of the present application have conducted intensive studies on a material capable of suppressing the area covered by the catalyst. As a result, it was found for the first time that the use of inherently microporous Polymers (PIMs) is advantageous in reducing the overvoltage of the electrode catalyst of the water electrolysis cell.
Based on the above findings, the inventors of the present application have found a novel electrode catalyst for a water electrolysis cell as follows.
(summary of one embodiment of the present disclosure)
The electrode catalyst for a water electrolysis cell according to claim 1 of the present disclosure comprises:
catalyst and process for preparing the same
Neutral inherently microporous polymers.
According to mode 1, an electrode catalyst having a low overvoltage water electrolysis cell can be provided.
In aspect 2 of the present disclosure, for example, in the electrode catalyst for a water electrolysis cell according to aspect 1, the inherently microporous polymer may have a tertagine skeleton.
In aspect 3 of the present disclosure, for example, in the electrode catalyst for a water electrolysis cell according to aspect 1, the intrinsically microporous polymer may have a spirobiindane skeleton.
In aspect 4 of the present disclosure, for example, in the electrode catalyst for a water electrolysis cell according to aspect 1, the inherently microporous polymer may have a polyimide skeleton.
According to aspects 2 to 4, the electrode catalyst for the water electrolysis cell can suppress an increase in overvoltage.
The water electrolysis cell according to claim 5 of the present disclosure includes:
an anode electrode,
Cathode, and
an electrolyte membrane disposed between the anode and the cathode,
at least one selected from the group consisting of the anode and the cathode includes the electrode catalyst according to any one of aspects 1 to 4.
According to the 5 th aspect, the water electrolysis cell can suppress an increase in overvoltage.
In the 6 th aspect of the present disclosure, for example, in the water electrolysis cell according to the 5 th aspect, the electrolyte membrane may include a proton exchange membrane.
In the 7 th aspect of the present disclosure, for example, in the water electrolysis cell according to the 5 th aspect, the electrolyte membrane may include an anion exchange membrane.
According to aspects 6 and 7, the oxygen gas generated at the anode and the hydrogen gas generated at the cathode are not easily mixed.
The water electrolysis cell according to claim 8 of the present disclosure includes:
a diaphragm separating the first space from the second space,
An anode disposed in the first space, and
a cathode disposed in the second space,
at least one selected from the group consisting of the anode and the cathode includes the electrode catalyst according to any one of aspects 1 to 4.
According to the 8 th aspect, the water electrolysis cell can suppress an increase in overvoltage.
The water electrolysis apparatus according to claim 9 of the present disclosure includes:
the hydrolysis cell according to any one of aspects 5 to 8, and a voltage applicator,
The voltage applicator is connected to the anode and the cathode and applies a voltage between the anode and the cathode.
According to the 9 th aspect, the water electrolysis apparatus can suppress an increase in overvoltage.
Embodiments of the present disclosure will be described below with reference to the drawings. The present disclosure is not limited to the following embodiments.
(embodiment 1)
Fig. 1 is a view schematically showing an electrode catalyst of a water electrolysis cell according to the present embodiment. The electrode catalyst 1 according to the present embodiment includes a catalyst 10 and a neutral inherently microporous Polymer (PIM) 11.PIM11 is present on at least a portion of the surface of catalyst 10. According to such a configuration, even if PIM11 is present on the surface of catalyst 10, the area of the surface on which catalyst 10 is exposed is less likely to be reduced, and the reduction in catalyst activity of electrode catalyst 1 can be suppressed. Therefore, when a voltage is applied to the electrode catalyst 1, an increase in overvoltage can be suppressed. That is, the electrode catalyst 1 can have a low overvoltage.
[ inherently microporous Polymer ]
Typically, the inherently microporous Polymer (PIM) 11 is an organic polymer having a specific molecular structure and having an inherent microporosity.
As described above, PIM11 is neutral. By "neutral" is meant that the molecule does not contain an anion exchange group or a cation exchange group. Examples of anion exchange groups are quaternary ammonium groups. Examples of cation exchange groups are sulfonic acid ionic groups.
PIM11 may be present on at least a portion of the surface of catalyst 10. The PIM11 may be present on a substrate on which the electrode catalyst 1 is to be formed, for example. Specifically, PIM11 may also be present on the surface of the substrate. By including the PIM11 in the electrode catalyst 1, the bonding force between the substrate and the catalyst 10 can be improved when the electrode catalyst 1 is formed on the substrate. Thus, the electrode catalyst 1 having high durability can be provided.
The PIM11 may also play a role in dispersing the electrode catalysts 1 from each other. In this case, by including PIM11 in electrode catalyst 1, electrode catalysts 1 can be prevented from agglomerating with each other.
The molecular structure of PIM11 is not limited to a specific molecular structure. Examples of the molecular structure include a tertagine skeleton, a spirobiindane skeleton and a polyimide skeleton.
The tertagine skeleton has, for example, a bicyclic compound containing 2 bridgehead nitrogen atoms. The nitrogen atom forms a chiral center. The tertagine scaffold may further have an ethylene-bridged anthracene (ethanoanthacrene) scaffold and a triptycene scaffold. Specifically, the tertagine skeleton has a molecular structure represented by the following general formula (1).
Figure BDA0004113874380000061
In the general formula (1), L represents a linker. The connector L is not limited to a specific structure. The linker L includes, for example, an aromatic ring, a spirobiindane skeleton, a bridge ethylene anthracene skeleton, and a triptycene skeleton.
The spirobiindane skeleton has, for example, 2 indanes. The 2 indanes form spiro compounds bonded through the center of the spiro atom. The spiro compound is a bicyclic organic compound, and one of atoms constituting a ring is shared with other rings. This atom is called a spiro atom. In the present disclosure, indane comprises, for example, a benzene ring bonded to a five-membered ring containing a spiro atom or a benzene ring bonded to a six-membered ring containing a spiro atom. Specifically, the spirobiindane skeleton has a molecular structure represented by the following general formula (2) or (3).
Figure BDA0004113874380000062
The polyimide skeleton is formed, for example, by polycondensation of an acid anhydride and a diamine. The anhydride and diamine may further comprise a spirobiindane skeleton, a bridge ethylene anthracene skeleton, and a triptycene skeleton. The polyimide skeleton has, for example, a molecular structure represented by the following general formula (4).
Figure BDA0004113874380000071
In the general formula (4), L represents a linker. The connector L is not limited to a specific structure. The linker L includes, for example, an aromatic ring, a spirobiindane skeleton, a bridge ethylene anthracene skeleton, and a triptycene skeleton.
Examples of PIM11 include an organic polymer having a tertagine skeleton, an organic polymer having a spirobiindane skeleton, and an organic polymer having a polyimide skeleton. The specific molecular structure of PIM11 may include at least 1 skeleton selected from the group consisting of a tertagine skeleton, a spirobiindane skeleton, and a polyimide skeleton. These backbones may have inherent microporosity. Further, these skeletons may be skeletons having high rigidity. By including these backbones in the molecular structure, PIM11 may have a desired porosity. PIM11 may have these backbones in the main chain or may have these backbones in the side chain. PIM11 may have a tertagine skeleton, a spirobiindane skeleton, and a polyimide skeleton, and may further have other substituents. Examples of other substituents are halogen radicals, hydroxy radicals, alkyl radicals, alkoxy radicals, carboxyl radicals, ester radicals, acyl radicals, amino radicals, nitro radicals, sulfo radicals and aryl radicals. Examples of halogen groups are fluoro, chloro and bromo.
The PIM11 may include at least 1 organic polymer selected from the group consisting of an organic polymer having a tertagine skeleton, an organic polymer having a spirobiindane skeleton, and an organic polymer having a polyimide skeleton.
The average pore diameter of PIM11 is, for example, 4nm or less. The average pore diameter of PIM11 can be determined by N 2 The Brunauer-Emmett-Teller (BET) method of the gas adsorption method. The average pore diameter of PIM11 can be measured, for example, as follows. The sample containing PIM11 was degassed under reduced pressure at 100 ℃ for 15 hours using a pore distribution measuring device VacPrep 061 manufactured by shimadzu corporation. Then, an automatic specific surface area measuring device, i.e., a device II3020 manufactured by shimadzu corporation, was used, and the device was passed through N 2 The gas adsorption method can calculate the average pore diameter of PIM11 by performing pore distribution analysis.
[ catalyst ]
CatalystReference numeral 10 denotes a material which is active for a reaction of generating a gas such as hydrogen or oxygen in the anode or cathode of the water electrolysis cell. Examples of the catalyst 10 are metals and metal oxides. An example of a metal is Pt. Examples of metal oxides are Layered Double Hydroxides (LDH) and IrO x 。
LDHs comprise, for example, more than 2 transition metals. The transition metal includes, for example, at least 2 metals selected from the group consisting of V, cr, mn, fe, co, ni, cu, W and Ru.
LDH has a composition represented by, for example, the following composition formula (1).
[M 1 2+ 1-x M 2 3+ x (OH) 2 ][yA n- ·mH 2 O]Composition formula (1)
In the composition formula (1), M 1 2+ Is a divalent transition metal ion. M is M 2 3+ Is a trivalent transition metal ion. A is that n- Is an anion between layers. x is 0<x<Rational number of conditions of 1. y is a number corresponding to the amount required for charge balance. n is an integer. m is a suitable rational number.
LDH may comprise Ni and Fe. In the composition formula (1), M 1 May be Ni, and M 2 May be Fe. That is, the transition metal element contained in the LDH may be Ni or Fe. According to such a constitution, the electrode catalyst 1 can have a higher catalyst activity.
The ratio of the amount of Fe contained in the LDH to the total amount of Ni and Fe may be 0.25 or more and 0.5 or less. According to such a constitution, the electrode catalyst 1 can have a higher catalyst activity.
LDH may comprise a chelating agent. In this case, the chelating agent may coordinate to the transition metal ions in the LDH. This can further improve the dispersion stability of LDH. In addition, since LDHs contain chelating agents, LDHs with small particle sizes can be synthesized. As a result, the surface area of LDH can be increased, and thus the catalyst activity can be improved. The average particle diameter of LDH may be 100nm or less or 50nm or less. The average particle diameter of the LDH may be 10nm or less. The average particle size of LDH is the following value: when the particle size distribution of LDH obtained by the small angle X-ray scattering method (SAXS) is represented by a two-dimensional distribution chart showing the relationship between particle size and distribution, the area of the two-dimensional distribution chart is divided by the total particle number. The distribution is a value proportional to the total volume occupied by the number of particles of the particle size. The area of the two-dimensional distribution map is, for example, the product of the particle diameter and the number of particles corresponding to the particle diameter.
The chelating agent is not limited to a specific chelating agent. Chelating agents are for example organic compounds which coordinate to transition metals in LDHs. The chelating agent may be at least 1 organic ligand selected from the group consisting of bidentate organic ligands and tridentate organic ligands. Examples of chelating agents are beta-diketones, beta-keto esters and hydroxycarboxylic acids. Examples of beta-diketones are acetylacetone (ACAC), trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, thiophenoyltrifluoroacetone, di-tert-valerylmethane, dibenzoylmethane and ascorbic acid. Examples of beta-keto esters are methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate and methyl 3-oxovalerate. Examples of hydroxycarboxylic acids and salts thereof are tartaric acid, citric acid, malic acid, gluconic acid, ferulic acid, lactic acid, glucuronic acid and salts thereof. The chelating agent may comprise at least 1 chelating agent selected from the group consisting of acetylacetone and trisodium citrate. The chelating agent may be at least 1 chelating agent selected from acetylacetone and trisodium citrate.
A n- Is interlayer ion. A is that n- Is an inorganic ion or an organic ion. Examples of inorganic ions are CO 3 2- 、NO 3 - 、Cl - 、SO 4 2- 、Br - 、OH - 、F - 、I - 、Si 2 O 5 2- 、B 4 O 5 (OH) 4 2- PO (Point of sale) 4 3- . Examples of organic ions are CH 3 (CH 2 ) n SO 4- 、CH 3 (CH 2 ) n COO - 、CH 3 (CH 2 ) n PO 4- CH (CH) 3 (CH 2 ) n NO 3- 。A n- Is an anion which is intercalated between layers of metal hydroxide together with water molecules. A is that n- The charge and the ion size of (a) are not limited to specific values. LDH may comprise 1 a n- May also contain a plurality of A n- 。
Fig. 2 is a diagram schematically showing an example of the crystal structure of LDH represented by the composition formula (1). As shown in FIG. 2, LDH20 is shown in M 1 2+ Or M 2 3+ Each vertex of the octahedron being the center has OH - Ions. The metal hydroxide is formed by [ M ] 1 2+ 1-x M 2 3+ x (OH) 2 ] x+ And (3) representing. The metal hydroxide has a layered structure in which hydroxide octahedral sharing edges are linked in two dimensions. Anions and water molecules are located between the layers of metal hydroxide. The metal hydroxide layer functions as a host layer 21, and anions and water molecules are intercalated as a guest layer 22. That is, the LDH20 has a sheet-like structure in which the host layers 21 of metal hydroxide and the guest layers 22 of anions and water molecules are alternately laminated. LDH20 has M contained in a layer of metal hydroxide 1 2+ Part of (2) is replaced by M 2 3+ And the structure is formed. Thus, the surface of LDH20 is typically positively charged.
[ Carrier ]
The electrode catalyst 1 may further comprise a support. According to such a configuration, since the catalyst 10 is stably disposed by the carrier for the catalyst 10, the catalyst activity of the electrode catalyst 1 is easily maintained high.
Typically, the carrier has electrical conductivity. The carrier is not limited to a specific material. Examples of supports are transition metals and carbon materials. Examples of transition metals are V, cr, mn, fe, co, ni, cu, W and Ru. Examples of the carbon material are acetylene black and Ketjen Black (KB).
The shape of the carrier is not limited to a specific shape. The carrier may be in the form of foam or particles.
The electrode catalyst 1 according to the present embodiment can be used in, for example, a proton exchange membrane type water electrolysis apparatus, an anion exchange membrane type water electrolysis apparatus, or an alkaline membrane type water electrolysis apparatus. The electrode catalyst 1 may be used in at least one member selected from the group consisting of an anode and a cathode in the above-described water electrolysis apparatus.
(embodiment 2)
Fig. 3 is a cross-sectional view schematically showing an example of the water electrolysis cell according to the present embodiment.
The water electrolysis cell 2 includes an electrolyte membrane 31, an anode 100, and a cathode 200. The electrolyte membrane 31 is disposed between the anode 100 and the cathode 200, for example. At least one selected from the anode 100 and the cathode 200 includes the electrode catalyst 1 described in embodiment 1.
The electrolyte membrane 31 may be an electrolyte membrane having ion conductivity. The electrolyte membrane 31 is not limited to a specific type. The electrolyte membrane 31 may comprise a proton exchange membrane. The electrolyte membrane 31 may be a proton exchange membrane. The electrolyte membrane 31 may contain an anion exchange membrane. The electrolyte membrane 31 may also be an anion exchange membrane. The electrolyte membrane 31 is configured such that oxygen gas generated in the anode 100 and hydrogen gas generated in the cathode 200 are not easily mixed.
Anode 100 includes, for example, a catalyst layer 30. The catalyst layer 30 may be provided on one main surface of the electrolyte membrane 31. The "principal surface" refers to the surface of the electrolyte membrane 31 having the largest area. The electrode catalyst contained in the catalyst layer 30 may be the electrode catalyst 1 of embodiment 1. In the anode 100, a porous and conductive gas diffusion layer 33 may be further provided on the catalyst layer 30.
Cathode 200 includes, for example, catalyst layer 32. The catalyst layer 32 may be provided on the other main surface of the electrolyte membrane 31. That is, the catalyst layer 32 may be provided on the main surface opposite to the main surface on which the catalyst layer 30 is provided, with respect to the electrolyte membrane 31. The catalyst metal that can be used in the catalyst layer 32 is not limited to a specific type. The electrode catalyst may be platinum or the electrode catalyst 1. In the cathode 200, a porous and conductive gas diffusion layer 34 may be further provided on the catalyst layer 32.
According to the above configuration, at least one selected from the anode 100 and the cathode 200 includes the electrode catalyst 1, so that the water electrolysis cell 2 can suppress an increase in overvoltage.
(embodiment 3)
Fig. 4 is a cross-sectional view schematically showing an example of the water electrolysis apparatus according to the present embodiment.
The water electrolysis device 3 includes a water electrolysis cell 2 and a voltage applicator 40. The water electrolysis cell 2 is similar to the water electrolysis cell 2 of embodiment 2, and therefore, the description thereof is omitted.
The voltage applicator 40 is connected to the anode 100 and the cathode 200 of the water electrolysis cell 2. The voltage applicator 40 is a device for applying a voltage to the anode 100 and the cathode 200 of the water electrolysis cell 2.
The potential in the anode 100 becomes high and the potential in the cathode 200 becomes low by the voltage applicator 40. The voltage applicator 40 is not limited to a specific type as long as it can apply a voltage between the anode 100 and the cathode 200. The voltage applicator 40 may be a device for adjusting the voltage applied between the anode 100 and the cathode 200. Specifically, when the voltage applicator 40 is connected to a direct current power source such as a battery, a solar cell, or a fuel cell, the voltage applicator 40 includes a DC/DC converter. When the voltage applicator 40 is connected to an AC power source such as an industrial power source, the voltage applicator 40 includes an AC/DC converter. The voltage applicator 40 may be a power-type power source that adjusts the voltage applied between the anode 100 and the cathode 200 and the current flowing between the anode 100 and the cathode 200 so that the power supplied to the water electrolysis apparatus 3 becomes a predetermined set value.
With the above configuration, the water electrolysis apparatus 3 can suppress an increase in overvoltage.
(embodiment 4)
Fig. 5 is a cross-sectional view schematically showing another example of the water electrolysis cell according to the present embodiment.
The water electrolysis cell according to the present embodiment is, for example, an alkaline water electrolysis cell 4 using an alkaline aqueous solution. In alkaline water electrolysis, an alkaline aqueous solution may be used. Examples of the alkaline aqueous solution include an aqueous potassium hydroxide solution and an aqueous sodium hydroxide solution.
The alkaline water electrolysis cell 4 includes an anode 300 and a cathode 400. The alkaline water electrolysis cell 4 further comprises an electrolysis cell 70, a first space 50 and a second space 60. The anode 300 is disposed in the first space 50. The cathode 400 is disposed in the second space 60. The alkaline water electrolysis cell 4 has a diaphragm 41. The diaphragm 41 is provided inside the electrolytic cell 70 to separate the first space 50 from the second space 60. At least one selected from the anode 300 and the cathode 400 includes the electrode catalyst 1.
The electrode catalyst 1 may be contained in the anode 300. The anode 300 may include, for example, a catalyst layer in which the electrode catalyst 1 is included.
The electrode catalyst 1 may be included in the cathode 400. The cathode 400 may include, for example, a catalyst layer in which the electrode catalyst 1 is included.
The separator 41 is, for example, a separator for alkaline water electrolysis.
The anode 300 may be disposed in contact with the separator 41, or may have a space between the anode 300 and the separator 41. The cathode 400 may be disposed in contact with the separator 41, or may have a space between the cathode 400 and the separator 41.
The alkaline water electrolysis cell 4 electrolyzes an alkaline aqueous solution to produce hydrogen and oxygen. An aqueous solution containing a hydroxide of an alkali metal or an alkaline earth metal may be supplied into the first space 50 of the alkaline water electrolysis cell 4. An alkaline aqueous solution may be supplied into the second space 60 of the alkaline water electrolysis cell 4. Hydrogen and oxygen are produced by electrolysis while discharging an alkaline aqueous solution of a predetermined concentration from the first space 50 and the second space 60.
According to the above configuration, at least one selected from the anode 300 and the cathode 400 includes the electrode catalyst 1, so that the alkaline water electrolysis cell 4 can suppress an increase in overvoltage.
(embodiment 5)
Fig. 6 is a cross-sectional view schematically showing another example of the water electrolysis apparatus according to the present embodiment.
The water electrolysis apparatus according to the present embodiment is, for example, an alkaline water electrolysis apparatus 5 using an alkaline aqueous solution. The alkaline water electrolysis apparatus 5 includes an alkaline water electrolysis cell 4 and a voltage applicator 40. The alkaline water electrolysis cell 4 is similar to the alkaline water electrolysis cell 4 of embodiment 4, and therefore, the description thereof is omitted.
The voltage applicator 40 is connected to the anode 300 and the cathode 400 of the alkaline water electrolysis cell 4. The voltage applicator 40 is a device for applying a voltage to the anode 300 and the cathode 400 of the alkaline water electrolysis cell 4.
According to the above configuration, the alkaline water electrolysis apparatus 5 can suppress an increase in overvoltage.
Examples
Hereinafter, the present disclosure will be described in more detail by way of examples. The following examples are examples of the present disclosure, and the present disclosure is not limited to the following examples.
Example 1
(production of Ni-Fe LDH on Ni Carrier)
A mixture comprising Ni-Fe LDH and Ni particles was produced as follows. First, a mixed solvent of water and ethanol (specialty reagent, manufactured by Fusifying and Wako pure chemical industries, ltd.) was prepared. The volume ratio of water to ethanol was 2:3. In this mixed solvent, nickel chloride hexahydrate (manufactured by fufufufebrile and photoplethysmogram) and iron chloride hexahydrate (manufactured by fufebrile and photoplethysmogram) were dissolved so that the total concentration of Ni ions and Fe ions became 1.0M and the ratio of the amount of Fe ions to the total amount of Ni ions and Fe ions became 0.33. "M" means mol/dm 3 . Further, acetylacetone (ACAC) as a chelating agent was added in an amount of one third of the total amount of Ni ions and Fe ions. The resulting solution was stirred for 30 minutes. Ni particles (US Research Nanomaterials, manufactured by Inc. and having a particle diameter of 40 nm) having the same mass as that of the Ni-Fe LDH produced when all of Ni and Fe contained in the solution are desirably reacted, are added to the solution. Next, in a solution containing Ni-Fe LDH and Ni particles, the amount of the substance which becomes chloride ions in the solution is 2 timesPropylene Oxide (POX) was added in an amount to act as a pH raising agent. The resulting solution was stirred for 1 minute. At this time, the POX gradually traps hydrogen ions in the solution, and thus the pH of the solution gradually increases. Therefore, after the obtained solution was left to stand for about 3 days, the mixture of Ni-Fe LDH and Ni particles of the target sample was recovered.
(production of PIM (1))
PIM (1) according to example 1 was produced with reference to non-patent document 2. 1mol equivalent of 4,4 '-diamino-3, 3' -dimethylbiphenyl was dissolved in 5mol equivalents of dimethoxymethane. The solution was cooled to 0 ℃. Next, 120mol equivalents of trifluoroacetic acid were added dropwise to the solution over 0.5 hour. The mixed solution was stirred at room temperature for 5 days. Next, the mixed solution was added to a vigorously stirred aqueous ammonium hydroxide solution, and left standing for 2 hours. The solid thus obtained was collected by filtration and washed with water, methanol and acetone in this order.
After washing, the solid was dissolved in chloroform, and methanol was further added to precipitate a polymer. This operation was repeated 2 times. The obtained polymer was dried by a vacuum oven, whereby PIM (1) according to example 1 was obtained. PIM (1) is an organic polymer represented by the following structural formula. PIM (1) is an organic polymer having a tertagine skeleton.
Figure BDA0004113874380000141
(preparation of sample for evaluation of catalyst Activity)
PIM (1) was mixed into the mixture of Ni-Fe LDH and Ni particles so that the mass ratio of the mixture of Ni-Fe LDH and Ni particles to PIM (1) became 20:1 and the total mass became 21 mg. To the obtained mixture, 1.05mL of chloroform (manufactured by Fusifying and Wako pure chemical industries, ltd., reagent grade) was added to prepare a liquid for catalyst ink. The catalyst ink according to example 1 was prepared by finely treating the liquid for catalyst ink with an ultrasonic homogenizer for 30 minutes. 10. Mu.L of the catalyst ink according to example 1 was dropped onto a rotating disk electrode, and dried at room temperature, whereby a sample for evaluating the catalyst activity according to example 1 was obtained.
Example 2
A sample for evaluating the catalyst activity of example 2 was obtained in the same manner as in example 1, except that PIM (2) was used as the organic binder instead of PIM (1). PIM (2) is an organic polymer represented by the following structural formula. PIM (2) is an organic polymer having a tertagine skeleton.
Figure BDA0004113874380000142
Example 3
A sample for evaluating the catalyst activity of example 3 was obtained in the same manner as in example 1, except that PIM (3) was used as the organic binder instead of PIM (1). PIM (3) is an organic polymer represented by the following structural formula. PIM (3) is an organic polymer having a tertagine skeleton.
Figure BDA0004113874380000151
Example 4
A sample for evaluating the catalyst activity of example 4 was obtained in the same manner as in example 1, except that PIM (4) was used as the organic binder instead of PIM (1). PIM (4) is an organic polymer represented by the following structural formula. PIM (4) is an organic polymer having a tertagine skeleton.
Figure BDA0004113874380000152
Example 5
(production of Ni-Fe LDH on Keqin Black Carrier)
Ni-Fe LDH was produced as follows. First, a mixed solvent of water and ethanol (specialty reagent, manufactured by Fusifying and Wako pure chemical industries, ltd.) was prepared. Water and method for producing sameThe volume ratio of ethanol was 2:3. In this mixed solvent, nickel chloride hexahydrate (manufactured by fufufufebrile and photoplethysmogram) and iron chloride hexahydrate (manufactured by fufebrile and photoplethysmogram) were dissolved so that the total concentration of Ni ions and Fe ions became 1.0M and the ratio of the amount of Fe ions to the total amount of Ni ions and Fe ions became 0.33. "M" means mol/dm 3 . Further, acetylacetone (ACAC) as a chelating agent was added in an amount of one third of the total amount of Ni ions and Fe ions. The resulting solution was stirred for 30 minutes. Then, propylene Oxide (POX) as a pH raising agent was added in an amount 2 times the amount of the substance that becomes chloride ions in the solution, and stirring was performed for 1 minute. At this time, the POX gradually traps hydrogen ions in the solution, and thus the pH of the solution gradually increases. Thus, LDH of the target sample was recovered after standing for about 3 days. The above LDH modulation method is an example, and is not limited to this example. Here, the particle size distribution of Ni-Fe LDH dispersed in the solution was obtained by the X-ray small angle scattering method (SAXS) using SmartLab manufactured by the company. The relationship between the obtained particle size and distribution is represented by a two-dimensional distribution chart, and the average particle size of LDH is determined by dividing the area of the two-dimensional distribution chart by the total particle number. The average particle size of the Ni-Fe LDH was 10nm.
The obtained Ni-Fe LDH was mixed with a matrix of kohler black EC600JD manufactured by kohler corporation so that the mass ratio of Ni-Fe LDH to kohler black was 2:1 and the total mass was 8.5mg, to prepare a Ni-Fe LDH supported on a kohler black carrier. In example 5, a sample for evaluating the catalyst activity of example 5 was obtained in the same manner as in example 1, except that ni—fe LDH supported on a ketjen black support was used.
Example 6
IrO manufactured by Takara Shuzo was used x SA100 replaces the mixture of Ni-Fe LDH and Ni particles, and IrO is used x And PIM (1) has a mass ratio of 5: 1. and the total mass is 6mgOtherwise, a sample for evaluating the catalyst activity of example 6 was obtained in the same manner as in example 1.
Comparative example 1
A sample for evaluating the catalyst activity of comparative example 1 was obtained in the same manner as in example 1, except that sustinion manufactured by Dioxide Materials was used as the organic binder instead of PIM (1).
Comparative example 2
A sample for evaluating the catalyst activity of comparative example 2 was obtained in the same manner as in example 1, except that FAA-3 manufactured by Fumatech was used as the organic binder instead of PIM (1) and 1.03mL of chloroform was used.
(evaluation of overvoltage of catalyst)
Overvoltage of the samples for evaluating the catalyst activity of each example and each comparative example was measured. For the measurement, a potentiostat Versat 4 manufactured by Princeton Applied Research and a rotating electrode AFE3T050GC manufactured by Pin Research were used. The current from the anodic reaction in the water electrolysis cell was measured by the Rotating Disk Electrode (RDE) method under the following measurement conditions. The anodic reaction is an oxygen evolution reaction. The results are shown in Table 1.
[ measurement conditions ]
Solution: 1M KOH solution
Potential: 1.0V to 1.65V (vs. Reversible Hydrogen Electrode (RHE))
Potential scan speed: 10mV/sec
Electrode rotation speed: 1500 revolutions per minute (rpm)
TABLE 1
Figure BDA0004113874380000171
Table 1 shows the measurement results of the overvoltage of the samples for evaluating the catalyst activities of examples 1 to 6 and comparative examples 1 and 2. Table 1 shows the overvoltage in cycle 1 of the redox reaction.
Catalyst inks according to examples 1 to 6 were used in oxidationWith low overvoltage in the original cycle. As a result, in the catalyst inks according to examples 1 to 6, an increase in overvoltage was suppressed. Since the inherently microporous polymer used as the organic binder in examples 1 to 6 had porosity, the catalyst could be exposed from the inherently microporous polymer. It is considered that the increase in overvoltage is thereby suppressed in the catalyst inks related to examples 1 to 6. Further, the catalyst ink related to example 6 has a low overvoltage in the redox cycle. It is known that even when IrO is used as a catalyst material having conductivity x The catalyst ink also has a low overvoltage.
On the other hand, the catalyst inks according to comparative examples 1 and 2 have a high overvoltage. In the catalyst ink according to comparative examples 1 and 2, the organic binder having porosity was not used. It is therefore considered that the organic binder covers the catalyst material, thereby degrading the catalyst activity.
Industrial applicability
The electrode catalyst of the water electrolysis cell according to the present disclosure can be used for a water electrolysis apparatus.
Description of the reference numerals
1. Electrode catalyst
2. Water electrolysis cell
3. Water electrolysis device
4. Alkaline water electrolysis cell
5. Alkaline water electrolysis device
10. Catalyst
11. Inherently microporous Polymers (PIM)
20 LDH
21. Main body layer
22. Guest layer
30. 32 catalyst layer
31. Electrolyte membrane
33. 34 gas diffusion layer
40. Voltage applicator
41. Diaphragm
50. A first space
60. Second space
70. Electrolytic cell
100. 300 anode
200. 400 cathode

Claims (9)

1. An electrode catalyst for a water electrolysis cell, comprising:
catalyst and process for preparing the same
Neutral inherently microporous polymers.
2. The electrode catalyst for a water electrolysis cell according to claim 1, wherein the intrinsically microporous polymer has a tertagine skeleton.
3. The electrode catalyst of the water electrolysis cell of claim 1, the intrinsically microporous polymer having a spirobiindane framework.
4. The electrode catalyst for a water electrolysis cell according to claim 1, wherein the inherently microporous polymer has a polyimide skeleton.
5. A water electrolysis cell comprising:
an anode electrode,
Cathode, and
an electrolyte membrane disposed between the anode and the cathode,
at least one selected from the group consisting of the anode and the cathode comprises the electrode catalyst of any one of claims 1 to 4.
6. The water electrolysis cell of claim 5, the electrolyte membrane comprising a proton exchange membrane.
7. The water electrolysis cell of claim 5, the electrolyte membrane comprising an anion exchange membrane.
8. A water electrolysis cell comprising:
a diaphragm separating the first space from the second space,
An anode disposed in the first space, and
a cathode disposed in the second space,
at least one selected from the group consisting of the anode and the cathode comprises the electrode catalyst of any one of claims 1 to 4.
9. A water electrolysis apparatus is provided with:
the water electrolysis cell according to any one of claims 5 to 8, and a voltage applicator,
The voltage applicator is connected to the anode and the cathode and applies a voltage between the anode and the cathode.
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