CN111304677A - Membrane electrode assembly and method for producing hydrogen by electrolysis - Google Patents

Membrane electrode assembly and method for producing hydrogen by electrolysis Download PDF

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CN111304677A
CN111304677A CN201911198355.5A CN201911198355A CN111304677A CN 111304677 A CN111304677 A CN 111304677A CN 201911198355 A CN201911198355 A CN 201911198355A CN 111304677 A CN111304677 A CN 111304677A
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catalyst
catalyst layer
anode
gas
cathode
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CN111304677B (en
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林国兴
蔡丽端
林有铭
赵文轩
黄秋萍
杨秉兴
黄筱君
林俊男
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Industrial Technology Research Institute ITRI
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention discloses a membrane electrode assembly and a method for producing hydrogen by electrolysis, wherein the method for producing hydrogen by electrolysis comprises the following steps: immersing a membrane electrode assembly in an alkaline aqueous solution, wherein the membrane electrode assembly comprises: an anode comprising a first catalyst layer on the first gas-liquid diffusion layer; the cathode comprises a second catalyst layer on the second gas-liquid diffusion layer; and an anion exchange membrane sandwiched between the anodesBetween the first catalyst layer and the second catalyst layer of the cathode, wherein the chemical structure of the first catalyst layer, the second catalyst layer, or both is MxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y is 2, wherein MxRuyN2Is cubic or amorphous; and applying a potential to the anode and the cathode to electrolyze the aqueous alkaline solution, so that the cathode generates hydrogen and the anode generates oxygen.

Description

Membrane electrode assembly and method for producing hydrogen by electrolysis
Technical Field
The invention relates to a membrane electrode assembly and a method for producing hydrogen by electrolysis by adopting a membrane electrolysis assembly.
Background
At present, the search for alternative energy is imperative, and hydrogen energy is the best alternative energy. Due to environmental protection concepts, the use of hydrogen as a fuel is expected to be environmentally friendly, and the electrolysis of water is the simplest way to produce hydrogen and oxygen. Although there are considerable advantages to hydrogen production by electrolysis of water, the process of producing hydrogen in large quantities has the fatal disadvantage of consuming considerable energy, resulting in non-compliance with costs. The energy consumption is often related to the overpotential, which is related to the electrodes, electrolyte, and reaction products. In order to improve the efficiency of water electrolysis, the electrodes play an important role. Lowering the activation energy and increasing the interface of the reaction are important factors for the efficiency of water electrolysis. The reduction in activation energy is effected by electrode surface catalysis, which depends on the catalytic properties of the electrode material itself. Although the noble metal Pt has been one of the most catalytically effective electrode materials, it is rather expensive. To reduce cost, other materials must be used in place of Pt.
In summary, a new catalyst (catalyst) composition is needed to further enhance the activities of the hydrogen production reaction (HER) and the oxygen production reaction (OER) so as to achieve the purposes of catalyst activity and cost reduction.
Disclosure of Invention
To achieve the above object, the present invention provides a membrane electrode assembly comprising: an anode comprising a first catalyst layer on the first gas-liquid diffusion layer; the cathode comprises a second catalyst layer on the second gas-liquid diffusion layer; and an anion exchange membrane sandwiched between a first catalyst layer of the anode and a second catalyst layer of the cathode, wherein the first catalyst layer, the second catalyst layer, or both have a chemical structure of MxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y is 2, wherein MxRuyN2Either cubic or amorphous.
In one embodiment, the membrane electrode assembly is immersed in an alkaline aqueous solution.
In one embodiment, M is Ni, 0.069< x <1.086, and 0.914< y < 1.931.
In one embodiment, M is Mn, 0.01< x <0.8, and 1.2< y < 1.99.
In one embodiment, MxRuyN2The surface appearance of the material is triangular pyramid and quadrangular pyramid.
In one embodiment, the first catalyst layer has a chemical structure of MxRuyN2The chemical structure of the second catalyst layer is MxRuyAnd M isxRuyIs a cubic system.
In one embodiment, the first gas-liquid diffusion layer and the second gas-liquid diffusion layer each comprise a porous conductive layer.
In one embodiment, the pore size of the first gas-liquid diffusion layer is between 40 microns and 150 microns, and the pore size of the second gas-liquid diffusion layer is between 0.5 microns and 5 microns.
The invention also provides a method for producing hydrogen by electrolysis, which comprises the following steps: immersing a membrane electrode assembly in an alkaline aqueous solution, wherein the membrane electrode assembly comprises: an anode comprising a first catalyst layer on the first gas-liquid diffusion layer; the cathode comprises a second catalyst layer on the second gas-liquid diffusion layer; and an anion exchange membrane sandwiched between the first catalyst layer of the anode and the second catalyst layer of the cathode, wherein the first catalyst layer and the second catalyst layerThe chemical structure of the two catalyst layers or both is MxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y is 2, wherein MxRuyN2Is cubic or amorphous; and applying a potential to the anode and the cathode to electrolyze the aqueous alkaline solution, so that the cathode generates hydrogen and the anode generates oxygen.
In one embodiment, the first catalyst layer has a chemical structure of MxRuyN2The chemical structure of the second catalyst layer is MxRuyAnd M isxRuyIs a cubic system.
Drawings
FIG. 1 is a schematic view of a membrane electrode assembly according to an embodiment;
FIG. 2 shows an example of Ru catalyst and NixRuyOER profile of the catalyst;
FIG. 3 shows an example of Ru2N2Catalyst NixRuyN2OER profile of the catalyst;
FIG. 4 shows an example of a Ru catalyst and NixRuyHER profile of the catalyst;
FIG. 5 shows an example of a Ru catalyst and NixRuyN2HER profile of the catalyst;
FIG. 6 shows an embodiment of Ni2N2Catalyst and MnxRuyN2OER profile of the catalyst;
FIG. 7 shows an embodiment of Ni2N2Catalyst and MnxRuyN2HER profile of the catalyst;
FIGS. 8, 9 and 11 are graphs of current-voltage curves of MEA in the example;
FIG. 10 is a graph of current flow after long term operation of a membrane electrode assembly in one example.
Description of the symbols
11 an anode;
11A, 15A gas-liquid diffusion layer;
11B, 15B catalyst layers;
13 an anion exchange membrane;
15a cathode;
100 membrane electrode assemblies.
Detailed Description
The nitride catalyst provided by one embodiment of the present invention has a chemical structure of: mxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y ═ 2, wherein the nitride catalyst is cubic or amorphous. If the nitride catalyst is of another crystal system, such as hexagonal crystal system, the catalytic effect on HER is lower than that of the commercially available Pt catalyst. In one embodiment, M is Ni, 0.069<x<1.086, for example: x is 0.0692-0.1128, 0.1128-0.1258, 0.1258-0.2012, 0.2012-0.318, 0.318-0.4672, 0.4672-0.6816, or 0.6816-1.086, and 0.914<y<1.931, for example: y is 1.9308-1.8872, 1.8872-1.8742, 1.8742-1.7988, 1.7988-1.682, 1.682-1.5328, 1.5328-1.3184, or 1.3184-0.914. In one embodiment, M is Mn, 0.01<x<0.8, and 1.2<y<1.99. If x is too small (i.e., y is too large), the activity and stability are poor. If x is too large (i.e., y is too small), the activity and stability are poor. In one embodiment, the surface topography of the nitride catalyst is triangular pyramid and quadrangular pyramid. This surface topography may contribute to the oxidation resistance of the nitride catalyst, i.e. suitable as anode for OER.
An embodiment of the present invention provides a method for forming a nitride catalyst, including: and placing the Ru target and the M target in an atmosphere containing nitrogen, wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu or Zn. Respectively providing power to the Ru target and the M target; and providing ions to impact the Ru target and the M target to sputter deposit MxRuyN2On a substrate, wherein 0<x<1.3，0.7<y<2, and x + y ═ 2, wherein the nitride catalyst is cubic or amorphous. In one embodiment, the nitrogen-containing atmosphere is at a pressure between 1mTorr and 30 mTorr. If the atmosphere pressure containing nitrogen is too low, the nitriding reaction cannot be efficiently performed. If containing nitrogen gasIf the atmospheric pressure of (2) is too high, an effective nitriding reaction cannot be performed. In one embodiment, the nitrogen-containing atmosphere comprises a carrier gas such as helium, argon, other suitable inert gas, or a combination thereof, and the partial pressure ratio of nitrogen to the carrier gas is between 0.1 and 10. If the partial pressure ratio of nitrogen is too low, the nitriding reaction cannot be efficiently performed. If the partial pressure ratio of nitrogen is too high, the nitriding reaction cannot be efficiently performed. The method provides power to the Ru target and the M target respectively. For example, the power supplied to the Ru target is between 10W and 200W. If the power supplied to the Ru target is too low, the Ru ratio in the nitride catalyst is too low. If the power supplied to the Ru target is too high, the Ru ratio in the nitride catalyst is too high. On the other hand, the power supplied to the M target is between 10W and 200W. If the power supplied to the M target is too low, the M ratio in the nitride catalyst is too low. If the power supplied to the M target is too high, the M ratio in the nitride catalyst is too high. The power may be direct current power or radio frequency power.
The method also provides ion bombardment of the Ru target and the M target to sputter deposit MxRuyN2On a substrate. For example, a plasma may be used to excite nitrogen and a carrier gas to form ions, and cause the ions to impact the target. In one embodiment, the substrate comprises a porous conductive layer, such as a porous metal mesh (e.g., a stainless steel mesh, a titanium mesh, a nickel alloy mesh, a niobium alloy mesh, a copper mesh, or an aluminum mesh) or a porous carbon material (e.g., a carbon paper or cloth). The pore diameter of the porous conductive layer depends on MxRuyN2The use of (1). For example, if there is MxRuyN2The porous conductive layer on the electrode is used as a cathode (for HER) for electrolyzing alkaline aqueous solution, and the pore diameter of the porous conductive layer is between 0.5 and 80 microns. If there is MxRuyN2The porous conductive layer on the conductive layer is used as an anode (for OER) for electrolyzing alkaline aqueous solution, and the pore diameter of the porous conductive layer is between 40 and 150 microns.
In one embodiment, the nitride catalyst may be used in membrane electrode assemblies for hydrogen electrolysis. As shown in FIG. 1, the membrane electrode assembly 100 includes an anode 11, a cathode 15, and an anionA proton exchange membrane 13, and an anion exchange membrane 13 is sandwiched between the anode 11 and the cathode 15. The anode 11 includes a catalyst layer 11B on the gas-liquid diffusion layer 11A, and the cathode 15 includes a catalyst layer 15B on the gas-liquid diffusion layer 15A. Furthermore, the method is simple. The anion exchange membrane 13 is interposed between the catalyst layer 11B of the anode 11 and the catalyst layer 15B of the cathode 15. The chemical structure of the catalyst layer 11B, the catalyst layer 15B, or both is MxRuyN2M, x, and y are as defined above and will not be repeated here.
In one embodiment, the anion exchange membrane 13 may be an imidazole polymer containing halogen ions or other suitable materials. For example, the anion exchange membrane 13 may be FAS available from Fumatech or X37-50 available from Dioxide materials. Since the membrane electrode assembly 100 is used for electrolyzing an alkaline aqueous solution to produce hydrogen, the anion exchange membrane 13 is used instead of other ion exchange membranes.
In one embodiment, the gas-liquid diffusion layer 11A and the gas-liquid diffusion layer 15A each include a porous conductive layer, such as a porous metal mesh (e.g., a stainless steel mesh, a titanium mesh, a nickel alloy mesh, a niobium alloy mesh, a copper mesh, an aluminum mesh) or a porous carbon material (e.g., a carbon paper or a carbon cloth). In one embodiment, the pore size of the gas-liquid diffusion layer 11A is between 40 microns and 150 microns. If the pore diameter of the gas-liquid diffusion layer 11A is too small, the mass transfer resistance increases. If the pore diameter of the gas-liquid diffusion layer 11A is too large, the active area is lost. In one embodiment, the pore size of the gas-liquid diffusion layer 15A is between 0.5 microns and 5 microns. If the pore diameter of the gas-liquid diffusion layer 15A is too small, the mass transfer resistance increases. If the pore diameter of the gas-liquid diffusion layer 15A is too large, the active area is lost. In some embodiments, the gas-liquid diffusion layer 11A may have the same pore diameter as the gas-liquid diffusion layer 15A, and the catalyst layer 11B and the catalyst layer 15B may have M in the same element ratioxRuyN2. In other words, the anode 11 and the cathode 15 can be the same electrode (gas-liquid diffusion layer with the same pore size and catalyst layer with the same element ratio) to save the processing procedure.
In other embodiments, the gas-liquid diffusion layer 11A of the anode 11 and the gas-liquid diffusion layer 15A of the cathode 15 have different pore diameters and/or different compositions, or the catalyst layer 11B of the anode 11 and the cathodeThe catalyst layers of the electrode 15 may have different elemental compositions or elemental proportions, as desired. For example, the chemical structure of the catalyst layer 11B is MxRuyN2The chemical structure of the catalyst layer 15B is MxRuyAnd M isxRuyIs a cubic system. In one embodiment, MxRuyThe surface topography of (2) is granular. In other embodiments, the anode 11 or cathode 15 may be a commercially available electrode (with other catalyst layers), while the catalyst layer of the other may be the nitride catalyst M described abovexRuyN2。
The membrane electrode assembly can be used for hydrogen production by electrolysis. For example, the membrane electrode assembly may be immersed in an aqueous alkaline solution. For example, the basic aqueous solution can be an aqueous solution of NaOH, KOH, other suitable bases, or combinations thereof. In one embodiment, the pH of the basic aqueous solution is greater than 14 and less than 15. If the pH of the alkaline aqueous solution is too low, the conductivity is not good. If the pH of the aqueous alkaline solution is too high, the solution viscosity becomes too high. The above method also applies a potential to the anode and the cathode to electrolyze the aqueous alkaline solution, causing the cathode to generate hydrogen gas and the anode to generate oxygen gas.
In conclusion, the nitride catalyst provided by the embodiment of the invention meets the requirement of electrolyzing alkaline aqueous solution to produce hydrogen. In the HER part, the nitride catalyst can solve the problems of poor catalytic effect, poor conductivity and low corrosion resistance of the existing catalyst. In the OER part, the nitride catalyst can solve the problems of poor catalytic effect, poor conductivity, low oxidation and corrosion resistance and the like of the existing catalyst. The nitride catalyst needs to have high conductivity and high HER and OER electrochemical activity. In the nitride catalyst of the embodiment of the present invention, in the diffusion viewpoint, the grain boundary diffusion coefficient at a low temperature is much larger than the bulk diffusion coefficient. Since the impurity atoms M added to the nitride catalyst may fill the grain boundaries, the diffusion of the atoms through the grain boundaries may be blocked, thereby improving the performance thereof. The fast diffusion paths of the nitride catalyst, such as grain boundaries, etc., may be filled with certain materials to prevent adjacent material atoms from diffusing through grain boundaries or other defects. By inserting nitrogen atoms into the grain boundary gap, the chance of diffusion of atoms through the grain boundary can be greatly reduced. In summary, the use of nitride can increase oxidation resistance and material stability. Because the nitride catalyst has good conductivity, Ru (which has activity similar to that of Pt) is combined with M to obtain the nitride catalyst with high conductivity and electrochemical activity under the condition of simultaneously taking the activity and the cost into consideration.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, several embodiments accompanied with figures are described in detail below:
examples
Preparation example 1
A reactive magnetron sputter was used to deposit Pt catalyst on a glassy carbon electrode (5mm OD. times.4 mm H). The Pt target was placed in a sputter tool, power was applied to the Pt target, and argon gas (flow rate 20sccm) was introduced into the tool at a pressure of 30 mTorr. Argon ions are used to impact a Pt target material and sputtering is carried out for 5 to 6 minutes at room temperature, so as to form a Pt catalyst with the film thickness of about 100nm on a glassy carbon electrode, and the coating amount of the catalyst is 0.042 mg.
Preparation example 2
Respectively depositing Ni with different element ratios on a glassy carbon electrode (5mm OD multiplied by 4mm H) by adopting a reaction magnetron sputtering machinexRuyA catalyst. The Ni target and the Ru target are placed in a sputtering machine, the power applied to the Ni target is adjusted between 10W and 200W and the power applied to the Ru target is adjusted between 10W and 200W, argon (the flow rate is 20sccm) is introduced into the machine, and the pressure in the machine is 20 mTorr. Argon ions are used to impact the Ni target and the Ru target to perform reactive sputtering for 5 to 6 minutes at room temperature to form Ni with a film thickness of about 100nmxRuyThe catalyst is coated on the glassy carbon electrode, and the coating amount of the catalyst is 0.024 mg. Analysis of Ni by EDSxRuyCatalyst, x is between about 0.065 to 0.85 and y is between about 1.935 to 1.15. Analysis of Ni by SEMxRuyThe surface appearance of the catalyst is granular. Analysis of Ni by X-ray diffraction (XRD)xRuyA catalyst which is cubic. On the other hand, the Ru target can be simply placed in a sputtering machine, and Ru catalyst with a film thickness of about 100nm is formed on the glassy carbon electrode by using similar parameters, and the coating amount of the catalyst is 0.024 mg.
Preparation example 3
Respectively depositing Ni with different element ratios on a glassy carbon electrode (5mm OD multiplied by 4mm H) by adopting a reaction magnetron sputtering machinexRuyN2A catalyst. Putting the Ni target and the Ru target into a sputtering machine, adjusting the power applied to the Ni target between 10 and 200W and the power applied to the Ru target between 10 and 200W, and introducing nitrogen and argon (the flow rate is 20sccm) into the machine, wherein the nitrogen/(argon + nitrogen) accounts for 50 percent, and the pressure in the machine is 20 mTorr. Argon ions are used to impact the Ni target and the Ru target to perform reactive sputtering for 5 to 6 minutes at room temperature to form Ni with a film thickness of about 100nmxRuyN2The catalyst is coated on the glassy carbon electrode, and the coating amount of the catalyst is 0.024 mg. Analysis of Ni by EDSxRuyN2Catalyst, x is between about 0.069 and 1.086, and y is between about 1.931 and 0.914. Analysis of Ni by SEMxRuyN2The surface appearance of the catalyst is triangular pyramid and quadrangular pyramid. Analysis of Ni by XRDxRuyN2A catalyst which is cubic or amorphous. On the other hand, the Ru target can be placed in the sputter tool to form Ru with a film thickness of about 100nm by similar parameters2N2The catalyst is coated on the glassy carbon electrode, and the coating amount of the catalyst is 0.024 mg.
Example 1
Mixing the above Pt, Ru and Ru2N2、NixRuyAnd NixRuyN2Catalyst, OER electrochemical activity test was performed as follows. Respectively taking Pt, Ru and Ru in 0.1MKOH solution2N2、NixRuyAnd NixRuyN2The glassy carbon electrode on which the catalyst was formed served as the working electrode. Hg/HgO was taken as a reference electrode and platinum was taken as an auxiliary electrode. The scanning voltage range is-0.8-1V, the scanning speed is 50mV/s, and the scanning times are 10 times. Then, the CV measurement of OER is performed, the scanning voltage range is-0.8-0.1V, the scanning speed is 10mV/s, and the scanning times are 5 times. The OER results are shown in FIG. 2(Ru and Ni)xRuy) FIG. 3 (Ru)2N2And NixRuyN2) As shown, the horizontal axis represents the potential (V) relative to the Reversible Hydrogen Electrode (RHE), and the vertical axis represents the current density (J, mA/cm)2). As shown in fig. 2, the pure Ru catalyst layer has no OER activity, while the Ru catalyst with Ni addition has significantly improved activity. As shown in FIG. 3, Ru2N2The catalyst activity is much higher than that of Ru catalyst, and Ru with a proper amount of Ni is added2N2Catalyst (i.e. Ni)xRuyN2Catalyst) activity can be greatly improved. For example, NixRuyN2X of (2) is between 0.4 and 1.1, which is preferable. A comparison of partial catalysts is shown in table 1:
TABLE 1
Figure BDA0002295243610000071
As can be seen from Table 1, Ni in OER0.29Ru1.71And Ni0.46Ru1.53N2The current density of the catalyst is higher than that of the platinum film catalyst. However NixRuyHas no oxidation resistance and is therefore not suitable for application in OER. In other words, Ni0.46Ru1.53N2More suitable for OER than platinum film catalysts.
Example 2
Mixing the above Pt, Ru and Ru2N2、NixRuyAnd NixRuyN2Catalyst, HER electrochemical activity test was performed as follows. Respectively taking Pt, Ru and Ru in 0.1MKOH solution2N2、NixRuyAnd NixRuyN2The glassy carbon electrode on which the catalyst was formed served as the working electrode. Hg/HgO was taken as a reference electrode and platinum was taken as an auxiliary electrode. In the HER measurement part, the rotating speed of the working electrode is 1600rpm, the scanning voltage range is 0-1V, the scanning speed is 10mV/s, and the scanning times are 3 times. The HER results are shown in FIG. 4(Ru and Ni)xRuy) FIG. 5(Ru and Ni)xRuyN2) The horizontal axis represents the potential (V) relative to the Reversible Hydrogen Electrode (RHE), and the vertical axis representsIs the current density (J, mA/cm)2). As shown in FIG. 4, Ni-added Ru catalyst (i.e., Ni)xRuy) The activity is obviously higher than that of the Ru catalyst. A comparison of partial catalysts is shown in table 2:
TABLE 2
Figure BDA0002295243610000081
As is clear from the above, Ni in HER0.06Ru1.93And Ni1.2Ru0.8N2The current density of the catalyst is higher than that of the platinum film catalyst. In other words, Ni0.29Ru1.71And Ni0.46Ru1.53N2The catalysts are all more suitable for HER than platinum film catalysts.
Preparation example 4
Respectively depositing Mn with different element ratios on a glassy carbon electrode (5mm OD multiplied by 4mm H) by adopting a reaction magnetron sputtering machinexRuyN2A catalyst. The Mn target and the Ru target are placed in a sputtering machine, the power (between 10 and 200W) applied to the Mn target and the power (between 10 and 200W) applied to the Ru target are adjusted, nitrogen and argon (the flow rate is 20sccm) are introduced into the machine, the nitrogen/(argon + nitrogen) is 50%, and the pressure in the machine is 20 mTorr. Argon ions are used to impact the Mn target and the Ru target, and reactive sputtering is carried out for 5 to 6 minutes at room temperature to form Mn with the thickness of about 100nmxRuyN2The catalyst is coated on the glassy carbon electrode, and the coating amount of the catalyst is 0.024 mg. Analysis of Mn by EDSxRuyN2Catalyst, x is between about 0.01 and 0.8 and y is between about 1.2 and 1.99. Analysis of Mn by SEMxRuyN2The surface appearance of the catalyst is triangular pyramid and quadrangular pyramid. Analysis of Mn by XRDxRuyN2A catalyst which is cubic or amorphous.
Example 3
Adding the above MnxRuyN2Catalyst, OER electrochemical activity test was performed as follows. Taking Mn in 0.1MKOH solutionxRuyN2Catalyst formThe glassy carbon electrode formed on the electrode is used as a working electrode. Taking Hg/HgO as a reference electrode, the rotating speed of a working electrode is 1600rpm, and taking platinum as an auxiliary electrode. The scanning voltage range is-0.8-1V, the scanning speed is 50mV/s, and the scanning times are 10 times. Then, the CV measurement of OER is performed, the scanning voltage range is-0.8-0.1V, the scanning speed is 10mV/s, and the scanning times are 5 times. The OER results are shown in FIG. 6 (Ni)2N2With MnxRuyN2) As shown, the horizontal axis represents the potential (V) relative to the Reversible Hydrogen Electrode (RHE), and the vertical axis represents the current density (J, mA/cm)2). As shown in FIG. 6, Ru was added in an appropriate amount2N2Catalyst (i.e. Mn)xRuyN2Catalyst) activity can be greatly improved. For example, MnxRuyN2X of (2) is between 0.3 and 0.7, which is preferred. A comparison of partial catalysts is shown in table 3:
TABLE 3
Figure BDA0002295243610000091
As can be seen from Table 3, Mn in OER0.323Ru1.677N2The current density of the catalyst is higher than that of the platinum film catalyst. In other words, Mn0.323Ru1.677N2The catalyst is more suitable for OER than the platinum film catalyst.
Example 4
Adding MnxRuyN2Catalysts were tested for HER electrochemical activity as follows. Taking Mn in 0.1MKOH solutionxRuyN2The glassy carbon electrode on which the catalyst was formed served as the working electrode. Hg/HgO was taken as a reference electrode and platinum was taken as an auxiliary electrode. In the HER measurement part, the rotating speed of the working electrode is 1600rpm, the scanning voltage range is 0-1V, the scanning speed is 10mV/s, and the scanning times are 3 times. The HER results are shown in FIG. 7, in which the horizontal axis represents the potential (V) relative to the Reversible Hydrogen Electrode (RHE) and the vertical axis represents the current density (J, mA/cm)2). A comparison of partial catalysts is shown in table 4:
TABLE 4
Figure BDA0002295243610000092
As described above, Mn in HER0.079Ru1.92N2The current density of the catalyst is higher than that of the platinum film catalyst. In other words, Mn0.079Ru1.92N2The catalyst is more suitable for HER than the platinum film catalyst.
Preparation example 5
Depositing Ni on a stainless steel mesh (316 stainless steel, 200mesh, 50mm x 50mm) by adopting a reaction magnetron sputtering machine0.75Ru1.25N2A catalyst. The Ni target and the Ru target were placed in a sputtering machine, the power applied to the Ni target (150W) and the power applied to the Ru target (100W) were adjusted, and nitrogen gas and argon gas (flow rate 10sccm) were introduced into the machine, where nitrogen gas/(argon gas + nitrogen gas) was 50%, and the pressure in the machine was 5 mTorr. Argon ions are used to impact the Ni target and the Ru target, and reactive sputtering is carried out for 8 minutes at room temperature to form Ni with the thickness of about 300nm0.75Ru1.25N2The catalyst (confirmed by EDS) was coated on a stainless steel mesh in an amount of 0.17mg/cm per unit area of the catalyst coating2. Analysis of Ni by SEM0.75Ru1.25N2The surface appearance of the catalyst is triangular pyramid and quadrangular pyramid. Analysis of Ni by XRD0.75Ru1.25N2A catalyst which is cubic or amorphous.
Example 5
Taking Ni of preparation example 50.75Ru1.25N2Stainless steel mesh as cathode for HER, commercially available DSA insoluble anode (IrO)2/RuO2Ti mesh, google energy technologies, inc.) as the anode of the OER, and an anion exchange membrane X37-50 (available from Dioxide Materials) was sandwiched between the catalyst layers of the cathode and anode to form a membrane electrode assembly. The membrane electrode assembly was immersed in 2M KOH solution and tested for electrochemical activity as follows. The scanning voltage range is 1.3-2.2V, and the scanning speed is 50 mV/s. The current-voltage curve of the mea is shown in fig. 8, and a current of 1.35A can be generated at 2V.
Example 6
Taking Ni of preparation example 50.75Ru1.25N2Stainless steel mesh serves both as the cathode for HER and the anode for OER, and an anion exchange membrane X37-50 (available from Dioxide Materials) is sandwiched between the catalyst layers of the cathode and anode to form a membrane electrode assembly. The membrane electrode assembly was immersed in 2M KOH solution and tested for electrochemical activity as follows. The scanning voltage range is 1.3-2.2V, and the scanning speed is 50 mV/s. The current-voltage curve of the mea is shown in fig. 9, and a current of 1.02A can be generated at 2V. The potential of the membrane electrode assembly was controlled to 2V and the operation was continued for 18 hours, and the current was stabilized as shown in fig. 10. In other words, Ni0.75Ru1.25N2The stainless steel mesh is effective against oxidation and can serve as an anode of OER.
Comparative example 1
A cathode was prepared by coating commercially available PtC (HISPEC 13100, Johnson Matthey) on H23C8(Freudenberg) carbon paper as HER, and controlling the coating amount per unit area of the cathode catalyst to 1.8mg/cm2Commercially available DSA insoluble anode (IrO)2/RuO2Ti mesh, google energy technologies, inc.) as the anode of the OER, and an anion exchange membrane X37-50 (available from Dioxide Materials) was sandwiched between the catalyst layers of the cathode and anode to form a membrane electrode assembly. The membrane electrode assembly was immersed in 2M KOH solution and tested for electrochemical activity as follows. The scanning voltage range is 1.3-2.2V, and the scanning speed is 50 mV/s. The current-voltage curve of the mea is shown in fig. 11, and a current of 1.3A can be generated at 2V.
The example 5, example 6, and comparison with the membrane electrode assembly of comparative example 1 are shown in table 5:
TABLE 5
Figure BDA0002295243610000111
As is clear from Table 5, Ni in examples 5 and 60.75Ru1.25N2The activity of the catalyst is far higher than that of PtC/IrO2/RuO2Activity of catalyst and amount of catalyst coating per unit area thereofPtC and IrO only2/RuO 21/10 for the amount of catalyst coating per unit area.
Although the present invention has been described in connection with the above embodiments, it is not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention.

Claims (10)

1. A membrane electrode assembly, comprising:
an anode comprising a first catalyst layer on the first gas-liquid diffusion layer;
the cathode comprises a second catalyst layer on the second gas-liquid diffusion layer; and
an anion exchange membrane sandwiched between the first catalyst layer of the anode and the second catalyst layer of the cathode,
wherein the first catalyst layer, the second catalyst layer, or both have a chemical structure MxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y is 2,
wherein M isxRuyN2Either cubic or amorphous.
2. The membrane electrode assembly of claim 1 immersed in an aqueous alkaline solution.
3. The mea of claim 1, wherein M is Ni, 0.069< x <1.086, and 0.914< y < 1.931.
4. The mea of claim 1, wherein M is Mn, 0.01< x <0.8, and 1.2< y < 1.99.
5. The mea of claim 1, wherein MxRuyN2The surface appearance of the material is triangular pyramid and quadrangular pyramid.
6. The mea of claim 1, wherein the first catalyst layer has a chemical structure MxRuyN2The chemical structure of the second catalyst layer is MxRuyAnd M isxRuyIs a cubic system.
7. The mea of claim 1, wherein the first gas-liquid diffusion layer and the second gas-liquid diffusion layer each comprise a porous conductive layer.
8. The mea of claim 1, wherein the first gdl has a pore size of 40-150 μm and the second gdl has a pore size of 0.5-5 μm.
9. A method for producing hydrogen by electrolysis, comprising:
immersing the membrane electrode assembly in alkaline aqueous solution,
wherein the membrane electrode assembly comprises:
an anode comprising a first catalyst layer on the first gas-liquid diffusion layer;
the cathode comprises a second catalyst layer on the second gas-liquid diffusion layer; and
an anion exchange membrane sandwiched between the first catalyst layer of the anode and the second catalyst layer of the cathode,
wherein the first catalyst layer, the second catalyst layer, or both have a chemical structure MxRuyN2Wherein M is Ni, Co, Fe, Mn, Cr, V, Ti, Cu, or Zn, 0<x<1.3，0.7<y<2, and x + y is 2,
wherein M isxRuyN2Is cubic or amorphous; and
applying a potential to the anode and the cathode to electrolyze the alkaline aqueous solution, so that the cathode generates hydrogen and the anode generates oxygen.
10. Such asMethod for the electrolytic production of hydrogen according to claim 9, wherein the chemical structure of the first catalyst layer is MxRuyN2The chemical structure of the second catalyst layer is MxRuyAnd M isxRuyIs a cubic system.
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