CN111534830B - Device and method for producing high-purity hydrogen by electrolyzing water - Google Patents

Device and method for producing high-purity hydrogen by electrolyzing water Download PDF

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CN111534830B
CN111534830B CN202010429122.8A CN202010429122A CN111534830B CN 111534830 B CN111534830 B CN 111534830B CN 202010429122 A CN202010429122 A CN 202010429122A CN 111534830 B CN111534830 B CN 111534830B
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anode chamber
sheet
electrode
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hydrogen
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CN111534830A (en
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王静
张帅帅
孙友财
樊玉蕾
陈宇辉
朱玉松
付丽君
吴宇平
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Nanjing Tech University
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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
    • 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
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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
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    • 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 device and a method for producing high-purity hydrogen by electrolyzing water. The device comprises an electrolytic cell, one end of a cathode chamber of the electrolytic cell is coated with an oxygen production catalyst RuO2One end of the Ti sheet seal and the anode chamber is coated with a hydrogen production catalyst Ni3The Ti sheet of the P is sealed, the Ti sheet of the cathode chamber and the Ti sheet of the anode chamber are oppositely butted, and an included angle is formed between the cathode chamber and the anode chamber at the butted position; the other ends of the cathode chamber and the anode chamber, which are far away from the butt joint part, are respectively provided with an air outlet; alkaline electrolyte is filled in the cathode chamber and the anode chamber, an auxiliary electrode NiOOH pole piece is arranged in the cathode chamber, and an auxiliary electrode Ni (OH) is arranged in the anode chamber2Pole piece, auxiliary electrode Ni (OH)2The pole piece and the NiOOH pole piece are connected with the positive pole and the negative pole of an external power supply. The method of the invention corresponds to the device. The invention thoroughly solves the problem of mixing hydrogen and oxygen in the process of electrolyzing water, and can uninterruptedly generate hydrogen to obtain high-purity hydrogen.

Description

Device and method for producing high-purity hydrogen by electrolyzing water
Technical Field
The invention belongs to the technical field of renewable energy sources, and particularly relates to a device and a method for producing high-purity hydrogen by electrolyzing water.
Background
With the rapid development of human society, people's demand for energy is increasing, but with the gradual exhaustion of non-renewable resources such as fossil fuels, such as coal, petroleum, natural gas, etc., people are urgently looking for renewable clean energy sources to replace fossil fuels.
Hydrogen is considered to be the most promising renewable energy source to replace fossil fuels. Compared with other energy sources, the hydrogen storage energy source has the advantages of high efficiency, environmental protection, high energy density and the like, and in addition, the product after the hydrogen combustion is water, so that the hydrogen storage energy source has no pollution to the environment and is considered as the optimal energy storage medium.
The hydrogen production by electrolyzing water is a method capable of utilizing renewable energy sources (such as wind energy, solar energy and the like) to produce hydrogen, but hydrogen produced by a cathode and oxygen produced by an anode are easy to mix in the electrolysis process, and the mixing of the hydrogen and the oxygen not only brings about a safety problem, but also increases the cost and energy consumption in the later gas purification process.
The principle of hydrogen production:
under acidic conditions
And (3) cathode reaction: h2O→1/2O2+2H++4e-
And (3) positive pole reaction: 2H++2e-→H2
Under alkaline conditions
And (3) cathode reaction: 4OH-→2H2O+O2+4e-
And (3) positive pole reaction: 2H2O+2e-→H2+2OH-。
In the field of hydrogen production by electrolysis of water, researchers have been searching for separate methods for producing hydrogen and oxygen. For example, a group of subjects of Yao Yuan uses an organic battery material PTPAn as a solid-state oxidation-reduction intermediate, hydrogen production and oxygen production are divided into two steps, and the hydrogen production and the oxygen production are separated in time. As another example, Leroy Cronin utilizes H3PMo12O40As electricityThe proton buffer solution separates hydrogen and oxygen generation in time in the process of water electrolysis, so that the aim of collecting pure hydrogen is fulfilled. However, these methods, while producing pure hydrogen, are not time-efficient, take twice as long to produce hydrogen, and may have residual gases in solution, resulting in hydrogen and oxygen mixing.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a device and a method for electrolyzing water to generate high-purity hydrogen, and aims to solve the problem of mixing of hydrogen and oxygen generated in the existing water electrolysis process by adopting a method of introducing an auxiliary electrode.
The invention is realized by that a device for electrolyzing water to generate high-purity hydrogen comprises an electrolytic cell, one end of a cathode chamber of the electrolytic cell is coated with an oxygen-producing catalyst RuO2One end of the Ti sheet seal and the anode chamber is coated with a hydrogen production catalyst Ni3The Ti sheet of the P is sealed, the Ti sheet of the cathode chamber and the Ti sheet of the anode chamber are oppositely butted, and an included angle is formed between the cathode chamber and the anode chamber at the butted position;
the other ends of the cathode chamber and the anode chamber, which are far away from the butt joint part, are respectively provided with an air outlet; wherein, alkaline electrolyte is filled in the cathode chamber and the anode chamber, an auxiliary electrode NiOOH pole piece is arranged in the cathode chamber, and an auxiliary electrode Ni (OH) is arranged in the anode chamber2Pole piece, auxiliary electrode Ni (OH)2The pole piece and the NiOOH pole piece are connected with the positive pole and the negative pole of an external power supply.
The invention further discloses a method for producing high-purity hydrogen by electrolyzing water, which comprises the following steps:
(1) by coating with an oxygen-generating catalyst RuO2The Ti sheet seals one end of the cathode chamber, and is coated with a hydrogen production catalyst Ni3One end of the anode chamber is sealed by the Ti sheet of P; butt-jointing Ti sheets of the cathode chamber and the anode chamber, and forming an included angle between the cathode chamber and the anode chamber at the butt-joint position;
(2) the other ends of the cathode chamber and the anode chamber, which are far away from the butt joint, are respectively provided with an air outlet, and the air outlets are arranged towards the cathode chamber and the anode chamberCharging alkaline electrolyte, placing auxiliary electrode NiOOH pole piece in the cathode chamber, placing auxiliary electrode Ni (OH) in the anode chamber2Pole pieces;
(3) connecting auxiliary electrode NiOOH pole piece with negative electrode of external power supply, and connecting auxiliary electrode Ni (OH)2The pole piece is connected with the positive pole of an external power supply, wherein oxygen is collected at the air outlet of the cathode chamber, and hydrogen is collected at the air outlet of the anode chamber.
Preferably, in step (1), the catalyst RuO will be contained2The oxygen-producing catalyst slurry is coated on a Ti sheet and vacuum-dried to obtain the oxygen-producing catalyst RuO2The Ti sheet of (1); will contain catalyst Ni3P hydrogen production catalyst slurry is coated on a Ti sheet, and vacuum drying is carried out to obtain Ni coated with hydrogen production catalyst3Ti pieces of P.
Preferably, the preparation process of the oxygen generating catalyst slurry is as follows: 65 to 85 parts by mass of RuO2Mixing with 10 parts by mass of a conductive agent, then adding 10 parts by mass of a binder and ethanol, and stirring to obtain oxygen-producing catalyst slurry; the preparation process of the hydrogen production catalyst slurry comprises the following steps: 65 to 85 parts by mass of Ni3And mixing the P and 10 parts by mass of a conductive agent, adding 10 parts by mass of a binder and ethanol, and stirring to obtain the hydrogen production catalyst slurry.
Preferably, RuO in the oxygen producing catalyst slurry2The content of (b) is 80 parts by mass; ni in hydrogen production catalyst slurry3The content of P was 80 parts by mass.
Preferably, the conductive agent is an acetylene black conductive agent, and the binder is a PTFE binder.
Preferably, in step (2), commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2And charging the electrode to obtain the NiOOH electrode.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) the invention thoroughly solves the problem of mixing hydrogen and oxygen in the process of electrolyzing water by a mode of generating oxygen in the cathode chamber and hydrogen in the anode chamber and separating the middle by the titanium metal plate, and can generate hydrogen uninterruptedly to obtain high-purity hydrogen;
(2) the invention adopts the commercial hydrogen-producing and oxygen-producing catalyst, can effectively reduce the overpotential in the water electrolysis process, and reduce the energy input;
(3) auxiliary electrode Ni (OH) used in the invention2And NiOOH when the cathode chamber NiOOH is completely reduced to Ni (OH)2When Ni (OH) in the anode chamber2When the NiOOH is completely oxidized, the electrodes of the cathode chamber and the anode chamber are exchanged, a new hydrogen production process can be carried out, and the method has the characteristics of high efficiency and energy saving;
(4) the invention utilizes the method of adding the auxiliary electrode, and realizes the separate hydrogen production and oxygen production by utilizing the advantages of the device under the condition of not greatly increasing the overpotential, and obtains high-purity hydrogen.
Drawings
FIG. 1 is a schematic view showing the construction of an apparatus for electrolyzing water to produce high-purity hydrogen according to the present invention;
FIG. 2 is an electrochemical curve of hydrogen production by electrolyzed water obtained in example 2 of the present invention;
fig. 3 is an overpotential diagram of an apparatus for electrolyzing water to generate high-purity hydrogen constructed in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
An apparatus for producing high-purity hydrogen by electrolyzing water, as shown in FIG. 1, comprises an electrolytic cell having a cathode chamber coated with Ni as hydrogen-producing catalyst at one end3 A Ti sheet 5 of P is sealed, one end of the anode chamber is coated with an oxygen generating catalyst RuO2The Ti sheet 6 of the cathode chamber is sealed, the Ti sheet 5 of the cathode chamber and the Ti sheet 6 of the anode chamber are oppositely butted, and an included angle is formed between the cathode chamber and the anode chamber at the butted position;
the anode chamber and the cathode chamber are far away from the pairThe other end of the joint is respectively provided with an air outlet 1 and an air outlet 2; wherein, alkaline electrolyte is filled in the cathode chamber and the anode chamber, an auxiliary electrode NiOOH pole piece 3 is arranged in the cathode chamber, and an auxiliary electrode Ni (OH) is arranged in the anode chamber2Pole piece 4, auxiliary electrode Ni (OH)2The pole piece 4 and the NiOOH pole piece 3 are connected with the positive and negative poles of an external power supply.
In the embodiment of the invention, after an included angle is formed between the cathode chamber and the anode chamber at the butt joint, the electrolytic cell is in a V shape, oxygen produced by the cathode chamber is discharged and collected through the air outlet 2, and hydrogen produced by the anode chamber is discharged and collected through the air outlet 1.
In the examples of the invention, the catalyst RuO will be contained2The oxygen-producing catalyst slurry is coated on a Ti sheet and vacuum-dried to obtain the oxygen-producing catalyst RuO2Ti plate 6; will contain catalyst Ni3P hydrogen production catalyst slurry is coated on a Ti sheet, and vacuum drying is carried out to obtain Ni coated with hydrogen production catalyst3Ti plate 5 of P.
In the embodiment of the present invention, the preparation process of the oxygen generating catalyst slurry is as follows: 65 to 85 parts by mass of RuO2Mixing with 10 parts by mass of a conductive agent, then adding 10 parts by mass of a binder and ethanol, and stirring to obtain oxygen-producing catalyst slurry; the preparation process of the hydrogen production catalyst slurry comprises the following steps: 65 to 85 parts by mass of Ni3And mixing the P and 10 parts by mass of a conductive agent, adding 10 parts by mass of a binder and ethanol, and stirring to obtain the hydrogen production catalyst slurry.
As a preferred configuration, and more specifically, RuO in an oxygen producing catalyst slurry2The content of (b) is 80 parts by mass; ni in hydrogen production catalyst slurry3The content of P was 80 parts by mass.
In the embodiment of the invention, the conductive agent is an acetylene black conductive agent, and the binder is a PTFE binder.
In the present example, commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2And charging the electrode to obtain the NiOOH electrode.
The invention is realized by arranging the cathodeThe method has the advantages that the problem of mixing hydrogen and oxygen in the water electrolysis process is thoroughly solved by means of room oxygen generation and hydrogen generation in the anode chamber and the separation of the middle by the titanium metal plate, and meanwhile, the hydrogen can be continuously generated to obtain high-purity hydrogen; in addition, the invention adopts commercial hydrogen-producing and oxygen-producing catalyst, which can effectively reduce the overpotential in the water electrolysis process and reduce the energy input; furthermore, the auxiliary electrode used in the present invention is Ni (OH)2And NiOOH when the cathode chamber NiOOH is completely reduced to Ni (OH)2When Ni (OH) in the anode chamber2When the NiOOH is completely oxidized, the electrodes of the cathode chamber and the anode chamber are exchanged, a new hydrogen production process can be carried out, and the method has the characteristics of high efficiency and energy saving; finally, the invention utilizes the method of adding the auxiliary electrode, and realizes the separate hydrogen production and oxygen production by utilizing the advantages of the device under the condition of not greatly increasing the overpotential, and obtains the high-purity hydrogen.
Example 2
(1) 80 parts by mass of RuO2And 10 parts by mass of a conductive agent, and then 10 parts by mass of a binder and ethanol (the amount of ethanol is such that the catalyst RuO is used2The conductive agent and the binder are required to be stirred into a slurry shape, for example, 40 to 80 parts by mass, and the following examples are explained as follows), and the mixture is stirred for 10 hours at room temperature to form oxygen-generating catalyst slurry; 80 parts by mass of Ni3Mixing the P and 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain hydrogen production catalyst slurry;
(2) respectively and uniformly coating 5mg of hydrogen production catalyst slurry and oxygen production catalyst slurry on Ti sheets with the thickness of 0.1cm and the length and width of 3cm, and performing vacuum drying at 70 ℃ for 24 hours to obtain Ti sheets coated with the two catalysts;
(3) taking 2.8g of KOH solid, adding 500mL of water to prepare 0.1M KOH solution;
(4) commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2Charging the electrode to obtain a NiOOH electrode;
(5) with Ni coated with hydrogen-generating catalyst3Ti plate of P will be chargedOne end of the anode chamber of the decomposition tank is sealed and coated with RuO serving as an oxygen production catalyst2One end of the cathode chamber of the electrolytic cell is sealed by the Ti sheet; butt-jointing Ti sheets of the cathode chamber and the anode chamber, forming an included angle between the cathode chamber and the anode chamber at the butt-joint position to form a V-shaped electrolytic cell, sealing the butt-joint position, adding alkaline electrolyte, and detecting that no liquid leakage exists;
(6) the resulting NiOOH electrode was combined with commercial Ni (OH)2Electrodes are respectively arranged at two ends of the V-shaped electrolytic tank and coated with Ni3One end of the P catalyst is provided with Ni (OH)2Pole pieces; coated with RuO2One end of the catalyst is provided with a NiOOH pole piece.
The electrochemical curve of hydrogen production by electrolyzed water obtained in this example is shown in FIG. 2, wherein RuO2-Ni3P means RuO2、Ni3Voltage of three electrode system consisting of P and reference electrode measured at different current densities, NiOOH-Ni (OH)2The finger is NiOOH, Ni (OH)2The voltage, NiOOH-RuO, of the three electrode system composed of reference electrode under different current densities2-Ni3P-Ni(OH)2Refers to the combination of NiOOH and RuO2Put in a solution system, Ni (OH)2And Ni3P was placed in another system with the same solution composition, and the two catalyst coated plates were connected by wire to the voltage measured at different current densities.
The above-mentioned steps are actually constructed as the apparatus for electrolyzing water to produce high-purity hydrogen as described in example 1, and thus, the overpotential diagram of the apparatus is shown in FIG. 3, in which RuO2-Ni3P+NiOOH-Ni(OH)2Refers to RuO2、Ni3Three-electrode system composed of P and reference electrode, NiOOH and Ni (OH)2The sum of the voltages measured at different current densities for the three electrode bodies consisting of the reference electrode, NiOOH-RuO2|Ni3P-Ni(OH)2Is the voltage measured by the device of the invention under different current densities.
Fig. 2 and 3 show the measurement of the voltage of the respective system at different current densities, for example: NiOOH-Ni (OH)2Namely, NiOOH pole piece, Ni (OH)2Pole piece and reference electrodePlacing in electrolyte to form a three-electrode system. After the vias were assembled, five different current densities (1 mA/cm) were given2、5mA/cm2、10mA/cm2、15mA/cm2、20mA/cm2) Measuring the corresponding voltage under the five current densities, and finally, taking the current density as an abscissa; the voltage is plotted on the ordinate to obtain the curve. Wherein "+" means the addition of voltages at the same current density for both systems, and the result of the addition is plotted against the current density; "|" refers to a metal sheet with catalyst supported on both sides.
As can be seen from FIGS. 2 and 3, the auxiliary electrode Ni (OH)2And NiOOH with Ni3P and RuO2The sum of the potentials of the electrolytic cells is equal to the potential of the four-electrode system used in this example.
Example 3
(1) 65 parts by mass of RuO2Mixing with 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain oxygen-producing catalyst slurry; 65 parts by mass of Ni3Mixing the P and 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain hydrogen production catalyst slurry;
(2) respectively and uniformly coating 7mg of hydrogen production catalyst slurry and oxygen production catalyst slurry on Ti sheets with the thickness of 0.1cm and the length and width of 3cm, and performing vacuum drying at 70 ℃ for 24 hours to obtain Ti sheets coated with the two catalysts;
(3) taking 2.8g of KOH solid, adding 500mL of water to prepare 0.1M KOH solution;
(4) commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2Charging the electrode to obtain a NiOOH electrode;
(5) with Ni coated with hydrogen-generating catalyst3One end of the anode chamber of the electrolytic cell is sealed by a Ti sheet of P, and the anode chamber is coated with RuO serving as an oxygen generation catalyst2One end of the cathode chamber of the electrolytic cell is sealed by the Ti sheet; the Ti sheet of the cathode chamber and the Ti sheet of the anode chamber are oppositely butted, and the cathode chamber and the anode chamber at the butted position are formedForming a V-shaped electrolytic cell at the included angle, sealing the butt joint, adding alkaline electrolyte, and detecting that no liquid leakage exists;
(6) the resulting NiOOH electrode was combined with commercial Ni (OH)2The electrodes are respectively arranged at two ends of the V-shaped electrolytic tank; coated with Ni3One end of the P catalyst is provided with Ni (OH)2Pole pieces; coated with RuO2One end of the catalyst is provided with a NiOOH pole piece.
Example 4
(1) 85 parts by mass of RuO2Mixing with 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain oxygen-producing catalyst slurry; 85 parts by mass of Ni3Mixing the P and 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain hydrogen production catalyst slurry;
(2) respectively and uniformly coating 9mg of hydrogen production catalyst slurry and oxygen production catalyst slurry on Ti sheets with the thickness of 0.1cm and the length and width of 3cm, and performing vacuum drying at 70 ℃ for 24 hours to obtain Ti sheets coated with the two catalysts;
(3) taking 2.8g of KOH solid, adding 500mL of water to prepare 0.1M KOH solution;
(4) commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2Charging the electrode to obtain a NiOOH electrode;
(5) with Ni coated with hydrogen-generating catalyst3One end of the anode chamber of the electrolytic cell is sealed by a Ti sheet of P, and the anode chamber is coated with RuO serving as an oxygen generation catalyst2The Ti sheet seals one end of the anode chamber of the electrolytic cell; butt-jointing Ti sheets of the cathode chamber and the anode chamber, forming an included angle between the cathode chamber and the anode chamber at the butt-joint position to form a V-shaped electrolytic cell, sealing the butt-joint position, adding alkaline electrolyte, and detecting that no liquid leakage exists;
(6) the resulting NiOOH electrode was combined with commercial Ni (OH)2The electrodes are respectively arranged at two ends of the V-shaped electrolytic tank; coated with Ni3One end of the P catalyst is provided with Ni (OH)2Pole pieces; coated with RuO2One end of the catalyst is provided with a NiOOH pole piece.
Example 5
(1) 65 parts by mass of RuO2Mixing with 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain oxygen-producing catalyst slurry; 65 parts by mass of Ni3Mixing the P and 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain hydrogen production catalyst slurry;
(2) respectively and uniformly coating 10mg of hydrogen production catalyst slurry and oxygen production catalyst slurry on Ti sheets with the thickness of 0.1cm and the length and width of 3cm, and performing vacuum drying at 70 ℃ for 24 hours to obtain Ti sheets coated with the two catalysts;
(3) taking 2.8g of KOH solid, adding 500mL of water to prepare 0.1M KOH solution;
(4) commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2Charging the electrode to obtain a NiOOH electrode;
(5) with Ni coated with hydrogen-generating catalyst3One end of the anode chamber of the electrolytic cell is sealed by a Ti sheet of P, and the anode chamber is coated with RuO serving as an oxygen generation catalyst2One end of the cathode chamber of the electrolytic cell is sealed by the Ti sheet; butt-jointing Ti sheets of the cathode chamber and the anode chamber, forming an included angle between the cathode chamber and the anode chamber at the butt-joint position to form a V-shaped electrolytic cell, sealing the butt-joint position, adding alkaline electrolyte, and detecting that no liquid leakage exists;
(6) the resulting NiOOH electrode was combined with commercial Ni (OH)2The electrodes are respectively arranged at two ends of the V-shaped electrolytic tank; coated with Ni3One end of the P catalyst is provided with Ni (OH)2Pole pieces; coated with RuO2One end of the catalyst is provided with a NiOOH pole piece.
Example 6
(1) 70 parts by mass of RuO2Mixing with 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain oxygen-producing catalyst slurry; 70 parts by mass of Ni3Mixing the P and 10 parts by mass of conductive agent, then adding 10 parts by mass of binder and ethanol, and stirring for 10 hours at room temperature to obtain hydrogen production catalyst slurry;
(2) respectively and uniformly coating 7mg of hydrogen production catalyst slurry and oxygen production catalyst slurry on Ti sheets with the thickness of 0.1cm and the length and width of 3cm, and performing vacuum drying at 70 ℃ for 24 hours to obtain Ti sheets coated with the two catalysts;
(3) taking 2.8g of KOH solid, adding 500mL of water to prepare 0.1M KOH solution;
(4) commercial Ni (OH)2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2Charging the electrode to obtain a NiOOH electrode;
(5) with Ni coated with hydrogen-generating catalyst3One end of the anode chamber of the electrolytic cell is sealed by a Ti sheet of P, and the anode chamber is coated with RuO serving as an oxygen generation catalyst2One end of the cathode chamber of the electrolytic cell is sealed by the Ti sheet; butt-jointing Ti sheets of the cathode chamber and the anode chamber, forming an included angle between the cathode chamber and the anode chamber at the butt-joint position to form a V-shaped electrolytic cell, sealing the butt-joint position, adding alkaline electrolyte, and detecting that no liquid leakage exists;
(6) the resulting NiOOH electrode was combined with commercial Ni (OH)2The electrodes are respectively arranged at two ends of the V-shaped electrolytic tank. Coated with Ni3One end of the P catalyst is provided with Ni (OH)2Pole pieces; coated with RuO2One end of the catalyst is provided with a NiOOH pole piece.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. An apparatus for producing high-purity hydrogen by electrolyzing water, which is characterized in that the apparatus comprises an electrolytic cell, one end of a cathode chamber of the electrolytic cell is coated with an oxygen-producing catalyst RuO2One end of the Ti sheet seal and the anode chamber is coated with a hydrogen production catalyst Ni3The Ti sheet of the P is sealed, the Ti sheet of the cathode chamber and the Ti sheet of the anode chamber are oppositely butted, and an included angle is formed between the cathode chamber and the anode chamber at the butted position;
the other ends of the cathode chamber and the anode chamber, which are far away from the butt joint part, are equally dividedAir outlet holes are respectively arranged; wherein, alkaline electrolyte is filled in the cathode chamber and the anode chamber, an auxiliary electrode NiOOH pole piece is arranged in the cathode chamber, and an auxiliary electrode Ni (OH) is arranged in the anode chamber2Pole piece, auxiliary electrode Ni (OH)2The pole piece and the NiOOH pole piece are connected with the positive pole and the negative pole of an external power supply.
2. A method for producing high purity hydrogen by electrolysis of water, comprising the steps of:
(1) by coating with hydrogen-generating catalyst Ni3One end of the anode chamber of the electrolytic cell is sealed by a Ti sheet of P, and the Ti sheet is coated with an oxygen generation catalyst RuO2One end of the cathode chamber of the electrolytic cell is sealed by the Ti sheet; butt-jointing Ti sheets of the cathode chamber and the anode chamber, and forming an included angle between the cathode chamber and the anode chamber at the butt-joint position;
(2) the other ends of the cathode chamber and the anode chamber, which are far away from the butt joint, are respectively provided with an air outlet, alkaline electrolyte is filled in the cathode chamber and the anode chamber, an auxiliary electrode NiOOH pole piece is arranged in the cathode chamber, and an auxiliary electrode Ni (OH) is arranged in the anode chamber2Pole pieces;
(3) connecting auxiliary electrode NiOOH pole piece with negative electrode of external power supply, and connecting auxiliary electrode Ni (OH)2The pole piece is connected with the positive pole of an external power supply, wherein oxygen is collected at the air outlet of the cathode chamber, and hydrogen is collected at the air outlet of the anode chamber.
3. The method for producing high-purity hydrogen by electrolyzing water as claimed in claim 2, wherein in the step (1), RuO containing catalyst is added2The oxygen-producing catalyst slurry is coated on a Ti sheet and vacuum-dried to obtain the oxygen-producing catalyst RuO2The Ti sheet of (1); will contain catalyst Ni3P hydrogen production catalyst slurry is coated on a Ti sheet, and vacuum drying is carried out to obtain Ni coated with hydrogen production catalyst3Ti pieces of P.
4. The method for producing high purity hydrogen by electrolysis of water according to claim 3, wherein the oxygen producing catalyst slurry is prepared by: 65 to 85 parts by mass of RuO2Mixing with 10 parts by mass of a conductive agent, then adding 10 parts by mass of a binder and ethanol, and stirring to obtain oxygen-producing catalyst slurry; the preparation process of the hydrogen production catalyst slurry comprises the following steps: 65 to 85 parts by mass of Ni3And mixing the P and 10 parts by mass of a conductive agent, adding 10 parts by mass of a binder and ethanol, and stirring to obtain the hydrogen production catalyst slurry.
5. The method of electrolyzing water to produce high purity hydrogen as in claim 4 wherein the RuO in the oxygen producing catalyst slurry2The content of (b) is 80 parts by mass; ni in hydrogen production catalyst slurry3The content of P was 80 parts by mass.
6. The method of electrolyzing water to produce high purity hydrogen as claimed in claim 4 wherein said conductive agent is acetylene black conductive agent and said binder is PTFE binder.
7. The method for producing high-purity hydrogen by electrolyzing water as claimed in claim 2, wherein in the step (2), commercial Ni (OH) is used2As a working electrode, a mercury-mercury oxide electrode as a reference electrode and a platinum sheet as a counter electrode to form a three-electrode system, and the counter electrode is Ni (OH)2And charging the electrode to obtain the NiOOH electrode.
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CN105463497A (en) * 2015-11-18 2016-04-06 复旦大学 Battery device capable of electrolyzing water for making hydrogen
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CN110117797A (en) * 2018-02-07 2019-08-13 中国科学院福建物质结构研究所 A kind of electrolytic cell and its application in water electrolysis hydrogen production

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CN105734600A (en) * 2016-03-19 2016-07-06 复旦大学 Three-electrode system double-electrolytic bath two-step water-electrolytic hydrogen producing device and method
CN110117797A (en) * 2018-02-07 2019-08-13 中国科学院福建物质结构研究所 A kind of electrolytic cell and its application in water electrolysis hydrogen production

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