CN109321936B - Device and method for producing hydrogen by electrolyzing water step by step based on liquid flow redox medium - Google Patents
Device and method for producing hydrogen by electrolyzing water step by step based on liquid flow redox medium Download PDFInfo
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Abstract
The invention belongs to the field of electrochemistry, and particularly relates to a device and a method for producing hydrogen by electrolyzing water step by step based on a liquid flow redox medium. The device for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium comprises: a diaphragm electrolytic cell-a, wherein the electrolyte of the anode chamber is an acid electrolyte and the electrolyte of the cathode chamber is an active medium electrolyte, and the active medium electrolyte is reduced in the electrolytic process and introduced into the following hydrogen evolution unit; a hydrogen evolution unit in which the active medium electrolyte originating from the cathode compartment of the diaphragm cell-a is oxidized while hydrogen is produced, and the oxidized active medium electrolyte is recycled back to the cathode compartment of the diaphragm cell-a. The invention adopts the liquid flow redox medium to couple the hydrogen evolution reaction with the oxygen evolution reaction so as to realize the precipitation of hydrogen and oxygen in different time and different space, thereby preparing high-purity hydrogen and completely avoiding the cross contamination of hydrogen and oxygen in the water electrolysis process.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a device and a method for producing hydrogen by electrolyzing water step by step based on a liquid flow redox medium.
Background
With the increasing world population and the rapid development of economy, people have more and more demand for energy. The energy is a material resource for providing various abilities and powers for human production and life, is an important material basis of national economy, and the control of the energy can determine future development fate of the country. In the face of the problems of energy shortage, increasingly severe environmental pollution and the like, the development of a clean, efficient and sustainable new energy power technology is urgent. Hydrogen energy has received much worldwide attention as a clean, efficient secondary energy source. The realization of large-scale and cheap hydrogen production lays a solid foundation for developing and utilizing hydrogen energy.
At present, 95% of hydrogen supplied industrially is prepared by high-temperature steam reforming of fossil fuels (natural gas, methanol and the like), the methods have the disadvantages of high energy consumption, high equipment requirement, high danger degree, low purity of prepared hydrogen and the like, and the water electrolysis hydrogen production technology is concerned because of low equipment requirement, no high pressure danger and high purity of prepared hydrogen. The hydrogen production by water electrolysis mainly comprises three types: alkaline electrolyzed water, proton exchange membrane electrolyzed water, and solid oxide electrolyzed water. The first industrialization is alkaline electrolysis water, because the cost is low, the technology is relatively mature; but the proton exchange membrane acid electrolyzed water has more outstanding advantages, firstly, the ohm reduction of an acid system is lower, the energy consumption is lower, the purity of the prepared hydrogen is higher, and the proton exchange membrane acid electrolyzed water can be more suitable for working under high current density and high pressure. The conditions for electrolyzing water by the solid oxide are harsh and need to be carried out under high temperature and high pressure. Much research is currently focused on developing more efficient Hydrogen Evolution (HER) and Oxygen Evolution (OER) catalysts, but it is more noteworthy that hydrogen and oxygen are produced simultaneously by the cathode and anode during the water electrolysis process, which is very likely to cause cross contamination of the two gases (especially at high current density and high pressure), resulting in impure produced hydrogen and increased pressure for subsequent purification. Although the ion selective exchange membrane can alleviate the problem of cross contamination of gases, the dynamics of oxygen evolution and hydrogen evolution are obviously different, so that the pressure at two sides of the diaphragm is different, and meanwhile, active oxygen species generated between the mixed gas and the catalyst can further enhance the degradation of the membrane, thereby greatly increasing the cost.
Disclosure of Invention
The invention aims to overcome the problems of the existing method for producing hydrogen by electrolyzing water, and provides a novel device and a novel method for producing hydrogen by electrolyzing water step by step based on a liquid flow redox medium.
Specifically, the device for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium comprises:
a diaphragm electrolytic cell-a, wherein the electrolyte of the anode chamber is an acid electrolyte and the electrolyte of the cathode chamber is an active medium electrolyte, and the active medium electrolyte is reduced in the electrolytic process and introduced into the following hydrogen evolution unit;
a hydrogen evolution unit in which the active medium electrolyte originating from the cathode compartment of the diaphragm cell-a is oxidized while hydrogen is produced, and the oxidized active medium electrolyte is recycled back to the cathode compartment of the diaphragm cell-a.
Further, the hydrogen evolution unit is a diaphragm electrolytic cell-b, the electrolyte of the anode chamber in the diaphragm electrolytic cell-b is an active medium electrolyte from the cathode chamber in the diaphragm electrolytic cell-a, the electrolyte of the cathode chamber is an acid electrolyte, the active medium electrolyte is oxidized in the electrolytic process, the cathode generates hydrogen, and the oxidized active medium electrolyte is recycled to the cathode chamber of the diaphragm electrolytic cell-a; alternatively, the first and second electrodes may be,
the hydrogen evolution unit is a chemical catalytic reaction tank, active medium electrolyte from the cathode chamber of the diaphragm electrolytic cell-a generates hydrogen through chemical catalytic reaction in the chemical catalytic reaction tank, and the oxidized active medium electrolyte circulates back to the cathode chamber of the diaphragm electrolytic cell-a.
When the oxidation-reduction potential of the active medium electrolyte is between the theoretical oxygen evolution potential and the hydrogen evolution potential of the electrolyzed water or is slightly lower than the theoretical hydrogen evolution potential of the electrolyzed water, the reduced medium can directly produce hydrogen through chemical catalysis without an additional electrochemical process, namely, the hydrogen evolution unit is a chemical catalysis reaction tank.
Further, the acid electrolytes in the anode chamber and the cathode chamber of the diaphragm electrolyzer-a and-b are independently selected from H2SO4Aqueous solution, H3PO4Aqueous solution and HClO4At least one of aqueous solutions.
Further, the concentration of the acid electrolyte in the diaphragm electrolytic cell-a and the diaphragm electrolytic cell-b is 0.5-5mol/L respectively and independently.
Further, the proton exchange membrane in the diaphragm electrolytic cell-a and the diaphragm electrolytic cell-b is selected from at least one of Nafion-115 membrane, Nafion-117 membrane and Nafion-122 membrane.
Further, the anode in the diaphragm electrolytic cell-a is an oxygen evolution catalytic electrode, and the cathode is a graphite/carbon felt electrode; the anode in the diaphragm electrolytic cell-b is a graphite/carbon felt electrode, and the cathode is a hydrogen evolution catalytic electrode.
Further, the oxygen evolution catalytic electrode is made of an oxygen evolution catalyst material selected from at least one of compounds of Ru, Ru alloys and Ru, compounds of Ir, Ir alloys and Ir, and compounds of Pt, Pt alloys and Pt.
Further, the hydrogen evolution catalytic electrode is made of a hydrogen evolution catalyst material selected from at least one of a noble metal simple substance, an alloy or a compound with carbon of Pt, Pd, Au and Ag, a Ni compound, a Co compound, an Fe compound, a Mo compound and a W compound.
Further, when the hydrogen evolution unit is a chemical catalytic reaction tank, the chemical catalytic reaction needs to adopt a hydrogen evolution catalyst material, and the hydrogen evolution catalyst material is selected from at least one of precious metal simple substances, alloys or compounds with carbon of Pt, Pd, Au and Ag, Ni compounds, Co compounds, Fe compounds, Mo compounds and W compounds.
Furthermore, the active medium electrolyte in the diaphragm electrolytic cell-a is at least one of heteropoly acid with multi-electron redox property and salt thereof, and organic small molecule with redox activity.
Further, the anion in the heteropoly acid and the salt thereof having the multiple electron redox property is selected from [ PMo12O40]3-、[SiMo12O40]4-、[GeMo12O40]4-、[PW12O40]3-、[SiW12O40]4-、[P2W18O40]6-、[P2Mo18O40]6-、[AlW12O40]3-、[ZnW12O40]6-、[CoW12O40]6-、[CuW12O40]6-And [ H2W12O40]6-And the cation is selected from H+、Li+、Na+And K+At least one of (1).
Further, the organic small molecule with redox activity is hydroquinone and/or hydroquinone derivatives.
Further, the device for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium also comprises an electrolyte storage tank for storing the active medium electrolyte, and the electrolyte storage tank is communicated with the cathode chamber of the diaphragm electrolytic cell-a. Before hydrogen production, the active medium electrolyte stored in the electrolyte storage tank needs to be pumped to the cathode chamber of the diaphragm electrolytic cell-a, and then the subsequent part of the electrolytic reaction is carried out.
The method for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium is carried out in the device for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium.
Further, when the hydrogen evolution unit is a diaphragm electrolyzer-b, the method comprises:
(1) oxygen production in diaphragm cell-a:
in the diaphragm cell-a, water molecules are electrochemically oxidized to oxygen at the anode surface, while the active medium electrolyte is reduced at the cathode surface, during which electrons are conducted from the anode to the cathode via an external circuit, while H is produced at the anode+The active medium electrolyte is reduced and simultaneously undergoes protonation and H combination by diffusing to a cathode through a proton exchange membrane+Then pumped to the anode chamber of the diaphragm electrolytic cell-b;
(2) hydrogen production in diaphragm cell-b:
in diaphragm cell-b, the active medium electrolyte is oxidized at the anode surface while H is present+Is electrochemically reduced to hydrogen gas at the cathode surface, during which electrons are conducted from the anode to the cathode through an external circuit, while H is generated from the active medium electrolyte+The electrolyte is diffused to the cathode through the proton exchange membrane, and the active medium electrolyte is pumped back to the cathode chamber of the diaphragm electrolytic cell-a after being oxidized.
Further, when the hydrogen evolution unit is a chemical catalytic reaction tank, the method comprises:
(1) oxygen production in diaphragm cell-a:
in the diaphragm cell-a, water molecules are electrochemically oxidized to oxygen at the anode surface, while the active medium electrolyte is reduced at the cathode surface, during which electrons are conducted from the anode to the cathode via an external circuit, while H is generated at the anode+The active medium electrolyte is reduced and simultaneously undergoes protonation and H combination by diffusing to a cathode through a proton exchange membrane+Then pumped to a chemical catalytic reaction tank;
(2) hydrogen production in a chemical catalytic reaction tank:
the active media electrolyte from the cathode compartment of the diaphragm cell-a is chemically catalyzed in a chemical catalytic reactor to produce hydrogen gas, the oxidized active media electrolyte of which is pumped back to the cathode compartment of the diaphragm cell-a.
The device and the method for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium couple hydrogen evolution reaction and oxygen evolution reaction by adopting the liquid flow redox medium, thereby realizing the precipitation of hydrogen and oxygen at different time and in different space. The hydrogen production process is divided into two steps, wherein the first step of oxidation-reduction medium is preferentially reduced before hydrogen evolution, electrons and protons generated by anodic water oxidation are stored at the same time, and then the second step of oxidation-reduction medium reversibly releases the electrons and the protons in the form of hydrogen through an electrochemical or direct chemical catalysis process, so that high-purity hydrogen is prepared, and the cross contamination of hydrogen and oxygen in the water electrolysis process can be completely avoided. In addition, the preparation device can work intermittently and also can work continuously, the degradation problem of the proton exchange membrane can be relieved, and the cost of hydrogen production by water electrolysis is further reduced.
Drawings
FIG. 1 is a schematic diagram of the operation of a hydrogen production plant based on the stepwise electrolysis of water by a liquid flow redox medium, wherein the hydrogen evolution unit is a diaphragm electrolyzer.
FIG. 2 is a schematic diagram of the operation of a hydrogen production device by water electrolysis step by step based on liquid flow redox media, wherein, the hydrogen evolution unit is a chemical catalytic reaction tank.
FIG. 3 is a graph of the electrolysis curve for the stepwise electrolysis of water to produce hydrogen based on a liquid flow redox mediator in example 1.
Description of the reference numerals
1-diaphragm electrolytic cell-a, 2-diaphragm electrolytic cell-b, 2 '-chemical catalytic reaction cell b', 3-electrolyte storage tank.
Detailed Description
The present invention will be described in more detail below.
As shown in fig. 1, the apparatus for producing hydrogen by stepwise water electrolysis based on liquid flow redox media according to the present invention is a dual-diaphragm electrolyzer apparatus, which includes:
the electrolytic cell comprises a diaphragm electrolytic cell-a 1, wherein the electrolyte of an anode chamber in the diaphragm electrolytic cell-a 1 is an acid electrolyte and the electrolyte of a cathode chamber is an active medium electrolyte, and the active medium electrolyte is reduced and introduced into an anode chamber of a diaphragm electrolytic cell-b in the electrolytic process;
the electrolyte of the anode chamber in the diaphragm electrolytic cell-b 2 is active medium electrolyte from the cathode chamber in the diaphragm electrolytic cell-a 1 and the electrolyte of the cathode chamber is acid electrolyte, the active medium electrolyte is oxidized in the electrolytic process and simultaneously generates hydrogen, and the oxidized active medium electrolyte is circulated back to the cathode chamber of the diaphragm electrolytic cell-a 1;
an electrolyte storage tank 3, wherein the electrolyte storage tank 3 is communicated with the cathode chamber of the diaphragm electrolytic cell-a 1 and is used for storing active medium electrolyte.
When the method for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium is carried out based on the double-diaphragm electrolytic cell, the method comprises the following steps:
(1) oxygen production in diaphragm cell-a 1: (with H)3PMo12O40Aqueous medium as an example)
In the diaphragm electrolyzer-a 1, water molecules are electrochemically oxidized to oxygen, H, at the anode surface2O–2e-→1/2O2+2H+(ii) a While the active medium electrolyte is reduced at the cathode surface, i.e. [ PMo ]12O40]3-+2e-+2H+→[H2PMo12O40]3-In the process, electrons pass from the anode through the external electricityPath-directed to cathode while anode produces H+Diffusion through the proton exchange membrane to the cathode, active mediator electrolyte [ PMo12O40]3-The protonation of the bound H takes place while being reduced+Generated [ H ]2PMo12O40]3-The solution is pumped to the anode chamber of the diaphragm electrolytic cell-b 2;
(2) hydrogen production in diaphragm electrolyzer-b 2:
in diaphragm cell-b 2, active Medium electrolyte [ H ]2PMo12O40]3-The solution is oxidized at the surface of the anode, i.e. [ H ]2PMo12O40]3--2e-→[PMo12O40]3-+2H+(ii) a At the same time H+Is electrochemically reduced to hydrogen gas, i.e. 2H, at the cathode surface++2e-→H2(ii) a In this process, electrons are conducted from the anode to the cathode through an external circuit, while [ H ]2PMo12O40]3-Solution generated H+Diffusion through the proton exchange membrane to the cathode to produce [ PMo12O40]3-Pumped back to the cathode compartment of the diaphragm cell-a.
As shown in fig. 2, the apparatus for producing hydrogen by stepwise electrolysis of water based on liquid flow redox media is a diaphragm electrolyzer + a chemical catalytic reactor, and comprises:
the electrolytic bath is characterized by comprising a diaphragm electrolytic bath-a 1, wherein the electrolyte of an anode chamber in the diaphragm electrolytic bath-a 1 is an acid electrolyte and the electrolyte of a cathode chamber is an active medium electrolyte, and the active medium electrolyte is reduced and introduced into a chemical catalytic reaction bath 2' in the electrolytic process;
a chemical catalytic reaction tank 2 ', wherein the active medium electrolyte from the cathode chamber of the diaphragm electrolytic cell-a 1 generates hydrogen through chemical catalytic reaction in the chemical catalytic reaction tank 2', and the oxidized active medium electrolyte is recycled to the cathode chamber of the diaphragm electrolytic cell-a 1;
an electrolyte storage tank 3, wherein the electrolyte storage tank 3 is communicated with the cathode chamber of the diaphragm electrolytic cell-a 1 and is used for storing active medium electrolyte.
When the device for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium is a diaphragm electrolytic cell + a chemical catalytic reaction cell, a hydrogen evolution catalyst is required to be adopted in the chemical catalytic reaction cell, and specifically, the hydrogen evolution catalyst can be selected from at least one of precious metal simple substances, alloys or compounds with carbon of Pt, Pd, Au and Ag, Ni compounds, Co compounds, Fe compounds, Mo compounds and W compounds.
When the method for producing hydrogen by electrolyzing water step by step based on the liquid flow redox medium is carried out based on the diaphragm electrolytic cell and the chemical catalytic reaction cell, the method comprises the following steps:
(1) oxygen production in diaphragm cell-a 1: (with H)4[SiW12O40]Aqueous medium as an example)
In the diaphragm electrolyzer-a 1, water molecules are electrochemically oxidized to oxygen, H, at the anode surface2O–2e-→1/2O2+2H+(ii) a While the active medium electrolyte is reduced at the cathode surface, i.e. H4SiW12O40+2e-+2H+→H6SiW12O40During this process, electrons are conducted from the anode to the cathode through an external circuit, while H is generated at the anode+Diffusing to the cathode through the proton exchange membrane, and the active medium electrolyte H4SiW12O40The protonation of the bound H takes place while being reduced+Generation of H6SiW12O40The solution is pumped to a chemical catalytic reaction tank b '2';
(2) hydrogen gas is produced in the chemical catalytic reaction tank b '2':
in the chemical catalytic reaction tank b '2', active medium electrolyte H6SiW12O40The solution is subjected to a chemical catalytic reaction in the presence of a catalyst to produce hydrogen, i.e. H6SiW12O40→H4SiW12O40+H2Generation of H4SiW12O40Is pumped back to the cathode compartment of the diaphragm cell-a 1.
The step (1) and the step (2) can work intermittently or continuously.
Based on the characteristic of liquid flow energy storage, the two steps can be operated continuously, so that the liquid flow redox media can be reduced and oxidized in the two diaphragm electrolytic cells, the preparation of hydrogen and oxygen in different electrolytic cells is realized, the cross contamination of the hydrogen and the oxygen is completely avoided, and the high-purity hydrogen is prepared. Meanwhile, the intermittent operation can be carried out, the surplus secondary energy can be pre-stored in the medium, and can be released in the form of hydrogen when needed.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The catalytic electrode for electrolyzing to generate oxygen in the double-diaphragm electrolytic cell device (figure 1) adopts a platinum mesh electrode, the catalytic electrode for electrolyzing to generate hydrogen is a platinum sheet electrode, and the active medium electrolyte in the cathode chamber in the diaphragm electrolytic cell-a is 0.02 mol/L H6[ZnW12O40]The electrolytes of the anode chamber in the diaphragm electrolytic cell-a and the cathode chamber in the diaphragm electrolytic cell-b are 0.5 mol/L sulfuric acid aqueous solution, the redox of the active medium electrolyte is carried out on a carbon cloth electrode, and the area of each electrode is 2 square centimeters. Firstly, in the diaphragm electrolytic cell-a, the anode is connected with a platinum mesh electrode, the cathode is connected with a carbon cloth electrode, and-0.56 Vvs. Ag/AgCl is applied on the carbon cloth electrode for constant potential reduction H6[ZnW12O40]The water solution and platinum mesh electrode produce oxygen. Then, H produced in the electrolytic cell-a6[H4ZnW12O40]Pumping the water solution into anode chamber of diaphragm electrolytic cell-b, connecting cathode with platinum sheet electrode and anode with carbon cloth electrode, and applying 0Vvs6[H4ZnW12O40]The aqueous solution is subjected to potentiostatic oxidation to regenerate H6[ZnW12O40]The aqueous solution is pumped back to the diaphragm electrolytic cell-a, and hydrogen is generated on the platinum sheet electrode. The coulomb efficiency calculated by the electric quantity passed by the two diaphragm electrolytic cells is as high as 95.3%. The purity of the gas produced was analyzed and the results showed that no cross-contamination of hydrogen and oxygen occurred at all. Wherein, the electrolysis graph of this example is shown in fig. 3, and it can be seen from fig. 3 that the two-step constant potential electrolysis method can exhibit excellent performance of electrolyzing water: reduction of H at a constant potential of-0.56 Vvs6[ZnW12O40]And then oxidizing at a constant potential of 0V vs. Ag/AgCl, wherein the coulombic efficiency can reach 95.3%, and the adopted medium has excellent redox reversibility. In addition, constant current electrolysis can be adopted for convenience of practical application operation.
Example 2
The catalytic electrode for generating oxygen by electrolysis in the diaphragm electrolytic cell and the chemical catalytic reaction cell device (figure 2) adopts an iridium oxide electrode, and the catalyst for chemically catalyzing and separating out hydrogen is 20% Pt/C (20 wt% Pt is loaded on carbon black, the same applies below) and 0.1 mol/L H6[ZnW12O40]The reduction of the aqueous solution is carried out on carbon cloth electrodes as a medium, the area of each electrode is 2 square centimeters, and the electrolyte of an anode chamber in the diaphragm electrolytic cell-a adopts 0.5 mol/L sulfuric acid aqueous solution. Firstly, in the diaphragm electrolytic cell-a, the anode is connected with an iridium oxide electrode, the cathode is connected with a carbon cloth electrode, and-0.56 Vvs. Ag/AgCl is applied on the carbon cloth electrode for constant potential reduction H6[ZnW12O40]The water solution and platinum mesh electrode produce oxygen. H produced in diaphragm cell-a6[H4ZnW12O40]The water solution is pumped to a chemical catalytic reaction tank b' through a pump and generates hydrogen under the physical mixing and magnetic stirring with 5mg of 20 percent Pt/C, thereby regenerating H6[ZnW12O40]The aqueous solution is pumped back to the diaphragm cell-a. Coulombic efficiency calculated from the hydrogen produced and the amount of electricity passed by the electrochemical process was as high as 95.5%. The purity of the gas produced was analyzed and the results showed that no cross-contamination of hydrogen and oxygen occurred at all.
Example 3
Diaphragm electrolyzer + chemical catalystThe catalytic electrode for generating oxygen by electrolysis in the reaction tank (figure 2) adopts an iridium oxide electrode, and the catalyst for chemically catalyzing and separating out hydrogen is 20% Pt/C and 0.1 mol/L H4[SiW12O40]The reduction of the aqueous solution is carried out on carbon cloth electrodes as a medium, the area of each electrode is 2 square centimeters, and the electrolyte of an anode chamber in the diaphragm electrolytic cell-a adopts 0.5 mol/L sulfuric acid aqueous solution. Firstly, in the diaphragm electrolytic cell-a, the anode is connected with an iridium oxide electrode, the cathode is connected with a carbon cloth electrode, and-0.56 Vvs. Ag/AgCl is applied on the carbon cloth electrode for constant potential reduction H4[SiW12O40]The water solution and platinum mesh electrode produce oxygen. H produced in diaphragm cell-a6[SiW12O40]The water solution is pumped to a chemical catalytic reaction tank b' through a pump and generates hydrogen under the physical mixing and magnetic stirring with 5mg of 20 percent Pt/C, thereby regenerating H6[SiW12O40]The aqueous solution is pumped back to the diaphragm cell-a. Coulombic efficiency calculated from the hydrogen produced and the amount of electricity passed by the electrochemical process reached 67.4%. The purity of the gas produced was analyzed and the results showed that no cross-contamination of hydrogen and oxygen occurred at all.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. An apparatus for producing hydrogen by stepwise electrolysis of water based on a liquid flow redox mediator, the apparatus comprising:
a diaphragm electrolytic cell-a, wherein the electrolyte of the anode chamber is an acid electrolyte and the electrolyte of the cathode chamber is an active medium electrolyte, and the active medium electrolyte is reduced in the electrolytic process and introduced into the following hydrogen evolution unit;
a hydrogen evolution unit in which the active medium electrolyte originating from the cathode compartment of the diaphragm cell-a is oxidized while producing hydrogen and the oxidized active medium electrolyte is recycled to the cathode compartment of the diaphragm cell-a; the hydrogen evolution unit is a chemical catalytic reaction tank, active medium electrolyte from the cathode chamber in the diaphragm electrolytic cell-a generates hydrogen through chemical catalytic reaction in the chemical catalytic reaction tank, and the oxidized active medium electrolyte circulates back to the cathode chamber of the diaphragm electrolytic cell-a; when the hydrogen evolution unit is a chemical catalytic reaction tank, the chemical catalytic reaction needs to adopt a hydrogen evolution catalyst, and the hydrogen evolution catalyst is selected from at least one of precious metal simple substances, alloys or compounds with carbon of Pt, Pd, Au and Ag, Ni compounds, Co compounds, Fe compounds, Mo compounds and W compounds;
the active medium electrolyte in the diaphragm electrolytic cell-a is heteropoly acid with multi-electron redox characteristics and salt thereof.
2. The apparatus for fractional electrolysis of water to produce hydrogen of claim 1, wherein the acid electrolyte in the anode compartment of diaphragm electrolyzer-a is selected from the group consisting of H2SO4Aqueous solution, H3PO4Aqueous solution and HClO4At least one of aqueous solutions.
3. The apparatus for fractional electrolysis of water to produce hydrogen according to claim 1, wherein the concentration of the acid electrolyte in the diaphragm cell-a is 0.5-5 mol/L.
4. The apparatus for fractional electrolysis of water to produce hydrogen based on a liquid flow redox mediator according to claim 1, wherein the proton exchange membrane in the diaphragm electrolyzer-a is selected from at least one of the group consisting of Nafion-115 membrane, Nafion-117 membrane and Nafion-122 membrane.
5. The apparatus for producing hydrogen by stepwise electrolysis of water based on a liquid flow redox mediator according to claim 1, wherein the anode of the diaphragm electrolyzer-a is an oxygen evolution catalytic electrode and the cathode is a graphite/carbon felt electrode.
6. The apparatus for producing hydrogen by the step-wise electrolysis of water according to claim 5, wherein the oxygen evolution catalytic electrode is made of an oxygen evolution catalyst material selected from at least one of Ru, Ru alloys and compounds of Ru, Ir alloys and compounds of Ir, Pt alloys and compounds of Pt.
7. The apparatus for fractional electrolysis of water for hydrogen production based on a liquid stream redox mediator according to any one of claims 1-6, wherein the anion in the heteropolyacid and salts thereof having multi-electron redox properties is selected from [ PMo ]12O40]3-、[SiMo12O40]4-、[GeMo12O40]4-、[PW12O40]3-、[SiW12O40]4-、[P2W18O40]6-、[P2Mo18O40]6-、[AlW12O40]3-、[ZnW12O40]6-、[CoW12O40]6-、[CuW12O40]6-And [ H2W12O40]6-And the cation is selected from H+、Li+、Na+And K+At least one of (1).
8. The apparatus for the fractional electrolysis of water to produce hydrogen based on a flowing redox medium of any one of claims 1-6, further comprising an electrolyte storage tank for storing an active medium electrolyte, said electrolyte storage tank being in communication with the cathode compartment of the diaphragm cell-a.
9. A method for producing hydrogen by water electrolysis step by step based on liquid flow redox medium, which is characterized in that the method is carried out in the device for producing hydrogen by water electrolysis step by step based on liquid flow redox medium according to any one of claims 1-8.
10. The process for fractional electrolysis of water to produce hydrogen based on a liquid stream redox medium of claim 9, wherein when the hydrogen evolution unit is a chemical catalytic reaction cell, the process comprises:
(1) oxygen production in diaphragm cell-a:
in the diaphragm cell-a, water molecules are electrochemically oxidized to oxygen at the anode surface, while the active medium electrolyte is reduced at the cathode surface, during which electrons are conducted from the anode to the cathode via an external circuit, while H is generated at the anode+The active medium electrolyte is reduced and simultaneously undergoes protonation and H combination by diffusing to a cathode through a proton exchange membrane+Then pumped to a chemical catalytic reaction tank;
(2) hydrogen production in a chemical catalytic reaction tank:
the active media electrolyte from the cathode compartment of the diaphragm cell-a is chemically catalyzed in a chemical catalytic reactor to produce hydrogen gas, the oxidized active media electrolyte of which is pumped back to the cathode compartment of the diaphragm cell-a.
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| CN111074291A (en) * | 2019-12-31 | 2020-04-28 | 西安泰金工业电化学技术有限公司 | Novel water electrolysis hydrogen production process |
| CN111346490B (en) * | 2020-03-18 | 2022-02-08 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
| CN111962091A (en) * | 2020-08-20 | 2020-11-20 | 上海电气集团股份有限公司 | Water electrolysis method and device |
| CN113088987A (en) * | 2021-02-25 | 2021-07-09 | 四川大学 | Device, system and method for directly trapping seawater to produce hydrogen based on proton-electricity coupling |
| CN113249737B (en) * | 2021-05-10 | 2022-03-18 | 张家港智电芳华蓄电研究所有限公司 | Battery for producing hydrogen by metal |
| CN113416972A (en) * | 2021-05-31 | 2021-09-21 | 复旦大学 | Device and method for producing hydrogen by electrolyzing water step by step based on all-vanadium liquid flow redox medium |
| CN113355680A (en) * | 2021-06-03 | 2021-09-07 | 中国科学技术大学 | Method and device for separating hydrogen and oxygen in electrolyzed water |
| CN113684488A (en) * | 2021-08-30 | 2021-11-23 | 四川大学 | Process for manufacturing new energy battery material and new energy hydrogen by carbon ferrochrome liquid phase method |
| CN113981467B (en) * | 2021-10-13 | 2023-03-31 | 西安交通大学 | Wide-pH step-by-step water electrolysis hydrogen production device and method based on sodium Prussian blue medium |
| CN114032571B (en) * | 2021-10-13 | 2022-12-09 | 西安交通大学 | Integrated system and method for coupling step-by-step water electrolysis device and water system battery |
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