CN113416972A - Device and method for producing hydrogen by electrolyzing water step by step based on all-vanadium liquid flow redox medium - Google Patents

Device and method for producing hydrogen by electrolyzing water step by step based on all-vanadium liquid flow redox medium Download PDF

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CN113416972A
CN113416972A CN202110596737.4A CN202110596737A CN113416972A CN 113416972 A CN113416972 A CN 113416972A CN 202110596737 A CN202110596737 A CN 202110596737A CN 113416972 A CN113416972 A CN 113416972A
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electrolytic cell
diaphragm electrolytic
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王永刚
孔涛逸
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Fudan 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention belongs to the technical field of water electrolysis, and particularly relates to a device and a method for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium. The plant comprises two diaphragm cells (cell 1 and cell 2), one hydrogen evolution unit and an acidic all vanadium electrolyte. The device comprises two steps of charging the all-vanadium redox flow battery by electrolyzing water and producing hydrogen and oxygen. First, VO of anode chamber in cell 12+Is oxidized into VO2 +While being introduced into the tank 2; and V of the cathode chamber in tank 13+Is reduced into V2+While being introduced into the hydrogen evolution unit. Second step, VO in cathode chamber in tank 22 +Is reduced into VO2+And is circulated back to the tank 1 whileThe anode generates oxygen; v2+Is oxidized to V in a hydrogen evolution unit3+And is circulated back to the tank 1 while generating hydrogen gas. The invention can realize the separation of hydrogen and oxygen in different spaces and time, thereby preparing high-purity hydrogen; meanwhile, the electrolytic voltage is reduced, and the volume of hydrogen production can be adjusted by controlling the amount of electrolyte.

Description

Device and method for producing hydrogen by electrolyzing water step by step based on all-vanadium liquid flow redox medium
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to a device and a method for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium.
Background
With the continuous progress of science and technology, the continuous development of national economy and military and the continuous improvement of the living standard of people, the demand of people on energy sources is higher and higher. Coal, oil and natural gas are the main energy sources at present, but the reserves of the fossil energy are limited, and a large amount of pollution and carbon emission are caused during the exploitation, development and use processes. In order to solve the contradiction between the energy shortage and the economic development and the environmental protection, the development of clean energy with wide sources, renewable property, low carbon and no pollution is necessary. It is also helpful for our country to achieve the goal of carbon neutralization in 2060 years. Hydrogen energy is a widely available, clean and low-carbon source of energy that is gaining favor worldwide. The large-scale and cheap development of hydrogen energy becomes an important target for scientific development.
The water electrolysis technology is mature, the operation is simple, the water electrolysis technology is clean and pollution-free, and the water resource sources on the earth are wide, so the water electrolysis becomes an important means for large-scale hydrogen production at present. The alkaline electrolyzed water is developed earliest, the technology is mature, and the industrialization is successful. However, the technology simultaneously generates hydrogen and oxygen at the cathode and the anode, and the obtained hydrogen has low purity and high risk coefficient. Then, acidic electrolyzed water of a proton exchange membrane is developed, so that gas generated by two electrodes can be effectively separated, and hydrogen with higher purity can be obtained. However, both gases are still produced in the same cell and at higher current densities and higher pressures, gas shuttling across the membrane still occurs. And the overpotential of hydrogen evolution and oxygen evolution is overcome during electrolysis, so that the electrolysis voltage is large and the requirement on current is high. We (Wang Yonggang, Xia Yongyao and Chenlong) have invented a method and a device (patent application number: 201510799110.3) for producing hydrogen by electrolyzing water based on a two-step method of a three-electrode system and a device and a method (patent application number: 201610164054.0) for producing hydrogen by electrolyzing water based on a two-step method of a three-electrode system and a double-electrolytic tank, so that the electrolytic preparation of separating hydrogen and oxygen in time and space is realized, and the mixing of gases is avoided. However, in the two methods, the mediators are solid electrodes, and the gas production volume is difficult to regulate in a large scale.
Disclosure of Invention
The invention aims to overcome the difficulty of water electrolysis, provides a method for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium, and reduces the electrolysis voltage of each step, so that hydrogen and oxygen are separately produced in two different electrolytic tanks, and high-purity hydrogen is obtained. Meanwhile, the liquid electrolyte is used as a redox mediator, so that the gas production volume is effectively regulated and controlled.
In the invention, the device for producing hydrogen by electrolyzing water step by step based on the oxidation-reduction medium of the all-vanadium liquid flow comprises: two independent diaphragm electrolytic cells and an independent hydrogen evolution unit; one diaphragm electrolytic cell is used for charging and discharging of the all-vanadium redox flow battery, the other diaphragm electrolytic cell is used for producing oxygen, and the hydrogen evolution unit is used for producing hydrogen. The technical scheme of the invention is specifically introduced as follows.
The invention provides a device for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium, which comprises a first diaphragm electrolytic cell for charging and discharging an all-vanadium redox flow battery, a second diaphragm electrolytic cell for producing oxygen and a hydrogen evolution unit for producing hydrogen; the hydrogen evolution unit is a third diaphragm electrolytic cell; the anode chamber of the first diaphragm electrolytic cell is in bidirectional communication with the cathode chamber of the second diaphragm electrolytic cell, and the cathode chamber of the first diaphragm electrolytic cell is in bidirectional communication with the anode chamber of the third diaphragm electrolytic cell; wherein:
the electrolyte in the anode chamber of the first diaphragm electrolytic cell is VO2+The electrolyte in the cathode chamber is V3+Acid of (2)
A solution;
the electrolyte in the anode chamber of the second diaphragm electrolytic cell is acidic electrolyte, and the electrolyte in the cathode chamber of the second diaphragm electrolytic cell is first diaphragm electrolyte
Electrolyte VO of anode chamber in electrolytic cell2+VO generated by oxidation reaction of acid solution2 +The solution and electrolyte in the cathode chamber of the second diaphragm electrolytic cell are subjected to reduction reaction to generate VO2+The solution is circulated back to the anode chamber of the first diaphragm electrolytic cell, and oxygen is generated in the anode chamber of the second diaphragm electrolytic cell;
the electrolyte in the anode compartment of the third diaphragm cell is derived from the cathode compartment electrolyte V in the first diaphragm cell3+Acid dissolution of
V generated by reduction reaction of liquid2+Solution, electrolysis in the anode compartment of a third diaphragm cellOxidation of biomass to form V3+The solution is circulated back to the cathode chamber of the first diaphragm electrolytic cell, the electrolyte in the cathode chamber of the third diaphragm electrolytic cell is acidic electrolyte, and hydrogen is generated in the cathode chamber of the third diaphragm electrolytic cell.
The invention also provides another device for producing hydrogen by electrolyzing water step by step based on the all-vanadium redox flow medium, which comprises a first diaphragm electrolytic cell for charging and discharging the all-vanadium redox flow battery, a second diaphragm electrolytic cell for producing oxygen and a hydrogen evolution unit for producing hydrogen; the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank; the anode chamber of the first diaphragm electrolytic cell is communicated with the cathode chamber of the second diaphragm electrolytic cell in a bidirectional way, and the cathode chamber of the first diaphragm electrolytic cell is communicated with the chemical catalytic solid-liquid reaction tank in a bidirectional way; wherein:
the electrolyte in the anode chamber of the first diaphragm electrolytic cell is VO2+The electrolyte in the cathode chamber is V3+Acid of (2)
A solution;
the electrolyte in the anode chamber of the second diaphragm electrolytic cell is acidic electrolyte, and the electrolyte in the cathode chamber of the second diaphragm electrolytic cell is first diaphragm electrolyte
Electrolyte VO of anode chamber in electrolytic cell2+VO generated by oxidation reaction of acid solution2 +The solution and electrolyte in the cathode chamber of the second diaphragm electrolytic cell are subjected to reduction reaction to generate VO2+The solution is circulated back to the anode chamber of the first diaphragm electrolytic cell, and oxygen is generated in the anode chamber of the second diaphragm electrolytic cell;
the reaction solution in the chemical catalysis solid-liquid reaction tank is derived from the electrolyte V in the cathode chamber in the first diaphragm electrolytic tank3+V generated by reduction reaction of acid solution2+Adding a hydrogen evolution catalyst into the chemical catalysis solid-liquid reaction tank to catalyze the solid-liquid chemical reaction, circulating the reaction solution after the reaction back to the cathode chamber of the first diaphragm electrolytic tank, and generating hydrogen in the chemical catalysis solid-liquid reaction tank.
In the invention, the electrolyte of the anode chamber of the second diaphragm electrolytic cell and the electrolyte of the cathode chamber of the third diaphragm electrolytic cell are respectively sulfuric acid, phosphoric acid, methanesulfonic acid and perchloric acid, and the concentration of the sulfuric acid is 1-5 mol/L, preferably 3 mol/L.
In the invention, the electrolyte supporting electrolyte of the first diaphragm electrolytic cell can be sulfuric acid, hydrochloric acid, phosphoric acid and methane sulfonic acid, and the concentration is 1-5 mol/L.
In the invention, the electrolyte in the cathode chamber of the first diaphragm electrolytic cell is vanadium (III) (V) sulfate2(SO4)3) The concentration is 0.5 to 3mol/L,
in the invention, the electrolyte in the anode chamber of the first diaphragm electrolytic cell Is Vanadyl (IV) sulfate (VOSO)4) The concentration is 0.5 to 3mol/L,
in the invention, the diaphragm of the first diaphragm electrolytic cell, the diaphragm of the second diaphragm electrolytic cell and the diaphragm of the third diaphragm electrolytic cell are independently selected from one of a Nafion membrane, a PBI membrane, a SPEEK membrane and a PAN porous membrane.
In the invention, the anode and the cathode of the first diaphragm electrolytic cell are all one of graphite felt, carbon paper and carbon cloth; the cathode of the second diaphragm electrolytic cell is one of graphite felt, carbon paper and carbon cloth, and the anode is an oxygen evolution catalytic electrode; the anode of the third diaphragm electrolytic cell is one of graphite felt, carbon paper and carbon cloth, and the cathode is a hydrogen evolution catalytic electrode.
In the invention, the oxygen evolution catalytic electrode has a catalytic effect on electrolyzing water to generate oxygen, and the electrode material with the catalytic effect is based on Ru, Ir or Pt noble metal, alloy and compound; or a simple substance or compound based on a transition metal of Ni, Co, Fe or Mn; or N, S, P doped carbon; or a bioelectrochemical catalyst, such as laccase.
In the invention, the hydrogen evolution catalytic electrode has a catalytic action on the generation of hydrogen by electrolyzing water, and the electrode material with the catalytic action is based on Pt, Pd, Au or Ag and a compound of the Pt, Pd, Au or Ag and carbon; or a simple substance or compound based on a transition metal of Ni, Co, or Fe; or compounds based on Cu, W, Mo; or C3N4A compound is provided.
In the present invention, the hydrogen evolution catalyst pair V2+The hydrogen ions are reduced to generate hydrogen gas with catalytic action, and the material with catalytic action is based on Pt, Pd, Au or Ag and a compound of the Pt, Pd, Au or Ag and carbon; or a simple substance or compound based on a transition metal of Ni, Co, or Fe; or compounds based on Cu, W, Mo;or C3N4A compound is provided.
In the invention, when the hydrogen evolution unit is a third diaphragm electrolytic cell for diaphragm electrolysis, the device also comprises 4 acid storage V2(SO4)3Electrolyte, acidic VOSO4The storage tanks are respectively communicated with the anode chamber of the first diaphragm electrolytic cell, the cathode chamber of the second diaphragm electrolytic cell, the cathode chamber of the first diaphragm electrolytic cell, the anode chamber of the third diaphragm electrolytic cell, the anode chamber of the second diaphragm electrolytic cell and the cathode chamber of the third diaphragm electrolytic cell; the storage tank and the tank are circulated by a pump.
In the invention, when the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank, the device also comprises 3 acid storage V2(SO4)3Electrolyte, acidic VOSO4The storage tanks are respectively communicated with the anode chamber of the first diaphragm electrolytic cell, the cathode chamber of the second diaphragm electrolytic cell, the cathode chamber of the first diaphragm electrolytic cell, the chemical catalysis solid-liquid reaction tank and the anode chamber storage tank of the second diaphragm electrolytic cell, and the storage tanks and the tanks are circulated through a pump.
The invention further provides an operation method of the step-by-step water electrolysis hydrogen production device based on the all-vanadium redox flow medium,
the method comprises the following specific steps:
when the first hydrogen evolution unit is a third diaphragm electrolytic cell
Charging an all-vanadium redox flow battery in a first diaphragm electrolytic cell:
v of cathode chamber in first diaphragm electrolytic cell3+Is electrochemically reduced to V2+VO of the anode compartment2+Is electrochemically oxidized into VO2 +(ii) a In the process, electrons are guided to the cathode from the anode through an external circuit, and hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm. Electrolyte from the anode compartment of the first diaphragm cell is then circulated to the cathode compartment of the second diaphragm cell and electrolyte from the cathode compartment of the first diaphragm cell is circulated to the anode compartment of the third diaphragm cell.
(II) electrolyzing the hydrogen and oxygen in the second diaphragm electrolytic cell and the third diaphragm electrolytic cell:
VO of cathode chamber in second diaphragm electrolytic cell2 +Is electrochemically reduced into VO2+Water is electrochemically oxidized into oxygen on the surface of the anode chamber oxygen evolution catalytic electrode; in the process, electrons are guided to the cathode by the anode through an external circuit, and simultaneously hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm. Subsequently the electrolyte in the cathode compartment of the second diaphragm cell is recycled to the anode compartment of the first diaphragm cell;
in the third diaphragm electrolytic cell, the anode chamber is electrochemically oxidized to form hydrogen ions on the surface of the hydrogen evolution catalytic electrode in the cathode chamber
Is electrochemically reduced to hydrogen; in the process, electrons are guided to the cathode by the anode through an external circuit, and simultaneously hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm. Subsequently the electrolyte in the anode compartment of the third diaphragm electrolytic cell is recycled to the cathode compartment of the first diaphragm electrolytic cell;
the electrolysis processes of the second diaphragm electrolytic cell and the third diaphragm electrolytic cell are carried out at different times or simultaneously;
the step (one) and the step (two) are alternately carried out;
when the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank
Charging an all-vanadium redox flow battery in a first diaphragm electrolytic cell:
v of cathode chamber in first diaphragm electrolytic cell3+Is electrochemically reduced to V2+VO of the anode compartment2+Is electrochemically implemented
Oxidation to VO2 +(ii) a In the process, electrons are guided to the cathode from the anode through an external circuit, and hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm. Then the electrolyte in the anode chamber of the first diaphragm electrolytic cell is circulated to the cathode chamber of the second diaphragm electrolytic cell, and the electrolyte in the cathode chamber of the first diaphragm electrolytic cell is circulated to the chemical catalytic solid-liquid reaction tank.
(II) oxygen generation by electrolysis in a second diaphragm electrolytic cell and hydrogen generation by catalysis in a chemical catalysis solid-liquid reaction tank:
VO of cathode chamber in second diaphragm electrolytic cell2 +Is electrochemically reduced into VO2+Water at the anodeIndoor oxygen evolution catalysis
The electrode surface is electrochemically oxidized to oxygen; in the process, electrons are guided to the cathode by the anode through an external circuit, and simultaneously hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm. Subsequently the electrolyte in the cathode compartment of the second diaphragm cell is recycled to the anode compartment of the first diaphragm cell;
in the chemical catalysis solid-liquid reaction tank, hydrogen ions are catalytically reduced to hydrogen gas V on the hydrogen evolution catalyst2+Is catalyzed by
Oxidation to V3+. Then the solution in the chemical catalysis solid-liquid reaction tank is circulated to the cathode chamber of the first diaphragm electrolytic tank;
the electrolysis process of the second diaphragm electrolytic cell and the chemical catalysis process of the chemical catalysis solid-liquid reaction cell are carried out at different times or
Simultaneously carrying out the steps;
the step (one) and the step (two) are alternately carried out.
Compared with the prior art, the invention has the beneficial effects that:
the electrolytic cell designed by the invention has the most remarkable characteristic that the electrolyzed water is decomposed into two steps of constant current electrolysis by using the all-vanadium redox flow medium, and the two steps of constant current electrolysis are separated in two independent cells in terms of time and space, so that high-purity hydrogen can be obtained at lower electrolysis voltage. Meanwhile, the volume of the hydrogen is adjusted by utilizing the adjustability of the volume concentration of the liquid medium.
Based on the method of the device, the charging and oxygen production and hydrogen production steps of the all-vanadium redox flow battery are alternately carried out, and the method is implemented
The recycling of the oxidation-reduction medium of the vanadium redox flow is realized, the electrolytic voltage is effectively reduced, the separate preparation of hydrogen and oxygen in different periods and different tanks is realized, and the high-purity hydrogen is finally obtained. Meanwhile, the purpose of adjusting the hydrogen yield can be achieved by adjusting the volume and the concentration of the all-vanadium liquid flow electrolyte.
Drawings
FIG. 1 is a three-diaphragm electrolytic cell step-by-step water electrolysis device using vanadium redox flow media.
FIG. 2 shows a step-by-step water electrolysis device with two diaphragm electrolytic cells and a single chemical catalytic solid-liquid reaction cell and all vanadium redox flow media.
FIG. 3 is a stepwise electrolysis curve for hydrogen and oxygen production.
Detailed Description
To further clearly illustrate the technical solutions and advantages of the present invention, the present invention is described by the following specific examples, but the present invention is not limited to these examples.
Example 1
The cathode of the tank 1 is connected with a storage tank and is placed with 10 ml of solution prepared by an electrolysis method and containing 1 mol/L V3+3mol/l H2SO4The anode is connected with a storage tank and is placed with 10 ml of VO with 1 mol/L2+3mol/l H2SO4And the cathode and anode electrodes are graphite felts treated for 24 hours at 400 ℃ in the air. The catalytic electrode for generating oxygen by the anode electrolysis of the tank 2 adopts an iridium dioxide/carbon composite electrode, the anode is connected with a storage tank and is placed with 10 ml of H with the concentration of 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. The hydrogen evolution unit adopts a diaphragm electrolytic cell 3, a catalytic electrode for generating hydrogen by cathode electrolysis of the cell 3 adopts a platinum mesh electrode, the cathode is connected with a storage tank and is placed with 10 ml of H with 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. All the electrode areas are 10 square centimeters, the diaphragm is made of 10 square centimeters Nafion117, and constant current electrolysis is carried out by adopting 500 milliamperes (50 milliamperes/square centimeter) of current. In the first step, cell 1 was electrolyzed for 1440 seconds with a voltage rise of about 1.6V, 1.52V on average, and then the cell 1 anode solution was pumped to the cell 2 cathode and the cell 1 cathode solution was pumped to the cell 3 anode. In the second step, cell 2 and cell 3 were electrolyzed, cell 2 voltage was raised to about 0.9V, average 0.56V, and cell 3 voltage was raised to about 0.4V, average 0.05V. The coulombic production efficiency calculated by dividing the second electrolytic electricity by the first electrolytic electricity is 89.93%, and the coulombic production efficiency is 90.56%. The purity of the generated gas is identified, and the fact that the oxyhydrogen gas is not mixed is proved. (FIG. 3)
Example 2
The cathode of the tank 1 is connected with a storage tank and is placed with 10 ml of solution prepared by an electrolysis method and containing 1 mol/L V3+3mol/l H2SO4The anode is connected with a storage tank and is placed in 10 mlContaining 1 mol/l VO2+3mol/l H2SO4And the cathode and anode electrodes are graphite felts treated for 24 hours at 400 ℃ in the air. The catalytic electrode for generating oxygen by the anode electrolysis of the tank 2 adopts a ruthenium dioxide/carbon composite electrode, the anode is connected with a storage tank and is placed with 10 ml of H with 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. The hydrogen evolution unit adopts a diaphragm electrolytic cell 3, a catalytic electrode for generating hydrogen by cathode electrolysis of the cell 3 adopts a platinum-carbon composite electrode, the cathode is connected with a storage tank and is placed with 10 ml of H with 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. All the electrode areas are 10 square centimeters, the diaphragm is a PBI film with 10 square centimeters, and constant current electrolysis is carried out by adopting 500 milliamperes (50 milliamperes/square centimeter) of current. In the first step, cell 1 was electrolyzed for 1440 seconds with a voltage rise of about 1.63V, 1.54V on average, and then the cell 1 anode solution was pumped to the cell 2 cathode and the cell 1 cathode solution was pumped to the cell 3 anode. In the second step, cell 2 and cell 3 were electrolyzed, cell 2 voltage was raised to about 0.9V, average 0.57V, and cell 3 voltage was raised to about 0.4V, average 0.06V. The coulombic efficiency for hydrogen production calculated by dividing the second electrolytic power by the first electrolytic power is 93.40%, and the coulombic efficiency for oxygen production is 94.02%. The purity of the generated gas is identified, and the fact that the oxyhydrogen gas is not mixed is proved.
Example 3
The cathode of the tank 1 is connected with a storage tank and is placed with 10 ml of solution prepared by an electrolysis method and containing 1 mol/L V3+3mol/l H2SO4The anode is connected with a storage tank and is placed with 10 ml of VO with 1 mol/L2+3mol/l H2SO4And the cathode and anode electrodes are graphite felts treated for 24 hours at 400 ℃ in the air. The catalytic electrode for generating oxygen by the anode electrolysis of the tank 2 adopts a ruthenium dioxide/carbon composite electrode, the anode is connected with a storage tank and is placed with 10 ml of H with 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. The hydrogen evolution unit adopts a chemical catalysis solid-liquid reaction tank, and the catalyst adopts molybdenum carbide particles. All the electrode areas are 10 square centimeters, the diaphragm is a 10 square centimeter Nafion117 film, and the current of 500 milliamperes (50 milliamperes/square centimeter) is adopted for constant currentAnd (4) electrolyzing by using electric current. In the first step, the cell 1 is electrolyzed for 1440 seconds, the voltage is increased to about 1.60V and the average voltage is 1.52V, then the anode solution of the cell 1 is pumped to the cathode of the cell 2, and the cathode solution of the cell 1 is pumped to the chemical catalysis solid-liquid reaction cell. Second stage of the cell 2 and simultaneous chemical catalysis H+And (3) reducing, wherein the voltage of the tank 2 is increased to about 0.9V, the average voltage is 0.54V, and the gas in the chemical catalytic solid-liquid reaction tank is collected by a drainage gas-collecting method to obtain 84 mL. The coulombic production efficiency calculated by dividing the second electrolytic electricity quantity by the first electrolytic electricity quantity is 93.55%, and the coulombic production efficiency determined according to the volume of the collected hydrogen is 92.01%. The purity of the generated gas is identified, and the fact that the oxyhydrogen gas is not mixed is proved.
Example 4
The cathode of the tank 1 is connected with a storage tank and 20 ml of the solution prepared by an electrolysis method and containing 1 mol/L V3+3mol/l H2SO4The anode is connected with a storage tank and is placed with 20 ml of VO with the concentration of 1 mol/L2+3mol/l H2SO4And the cathode and anode electrodes are graphite felts treated for 24 hours at 400 ℃ in the air. The catalytic electrode for generating oxygen by the anode electrolysis of the tank 2 adopts a ruthenium dioxide/carbon composite electrode, the anode is connected with a storage tank and is placed with 20 ml of H with the mol of 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. The hydrogen evolution unit adopts a chemical catalysis solid-liquid reaction tank, and the catalyst adopts molybdenum carbide particles. All the electrode areas are 10 square centimeters, the diaphragm is a 10 square centimeter Nafion117 film, and constant current electrolysis is carried out by adopting 500 milliamperes (50 milliamperes/square centimeter) of current. In the first step, the bath 1 is electrolyzed for 2880 seconds, the voltage is raised to about 1.57V and the average voltage is 1.49V, then the anode solution of the bath 1 is pumped to the cathode of the bath 2, and the cathode solution of the bath 1 is pumped to the chemical catalysis solid-liquid reaction bath. Second stage of the cell 2 and simultaneous chemical catalysis H+The voltage of the tank 2 is increased to about 0.88V and 0.53V on average after reduction, and the gas in the chemical catalytic solid-liquid reaction tank is collected by a drainage gas-collecting method to obtain 163 mL. The coulombic production efficiency calculated by dividing the second electrolytic electricity quantity by the first electrolytic electricity quantity is 93.55%, and the coulombic production efficiency determined according to the volume of the collected hydrogen is 89.27%. The purity of the generated gas is identified, and the fact that the oxyhydrogen gas is not mixed is proved.
Example 5
The cathode of the tank 1 is connected with a storage tank and is placed with 20 ml prepared by an electrolysis method and containing 0.5 mol/L V3+3mol/l H2SO4The anode is connected with a storage tank and is placed with 20 ml of VO with the concentration of 0.5 mol/L2+3mol/l H2SO4And the cathode and anode electrodes are graphite felts treated for 24 hours at 400 ℃ in the air. The catalytic electrode for generating oxygen by the anode electrolysis of the tank 2 adopts a ruthenium dioxide/carbon composite electrode, the anode is connected with a storage tank and is placed with 20 ml of H with the mol of 3mol/L2SO4The cathode electrode was a graphite felt treated at 400 ℃ for 24 hours under air. The hydrogen evolution unit adopts a chemical catalysis solid-liquid reaction tank, and the catalyst adopts molybdenum carbide particles. All the electrode areas are 10 square centimeters, the diaphragm is a PBI film with 10 square centimeters, and constant current electrolysis is carried out by adopting 500 milliamperes (50 milliamperes/square centimeter) of current. In the first step, the cell 1 is electrolyzed for 1440 seconds, the voltage is increased to about 1.60V and the average voltage is 1.51V, then the anode solution of the cell 1 is pumped to the cathode of the cell 2, and the cathode solution of the cell 1 is pumped to the chemical catalysis solid-liquid reaction cell. Second stage of the cell 2 and simultaneous chemical catalysis H+And (3) reducing, wherein the voltage of the tank 2 is increased to about 0.92V, the average voltage is 0.55V, and the gas in the chemical catalysis solid-liquid reaction tank is collected by a drainage gas-collecting method to obtain 85 mL. The coulombic production efficiency calculated by dividing the second electrolytic electricity quantity by the first electrolytic electricity quantity is 96.01%, and the coulombic production efficiency determined by the volume of the collected hydrogen is 97.57%. The purity of the generated gas is identified, and the fact that the oxyhydrogen gas is not mixed is proved.

Claims (10)

1. A device for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium is characterized by comprising a first diaphragm electrolytic cell for charging and discharging an all-vanadium redox flow battery, a second diaphragm electrolytic cell for producing oxygen and a hydrogen evolution unit for producing hydrogen; the hydrogen evolution unit is a third diaphragm electrolytic cell; the anode chamber of the first diaphragm electrolytic cell is in bidirectional communication with the cathode chamber of the second diaphragm electrolytic cell, and the cathode chamber of the first diaphragm electrolytic cell is in bidirectional communication with the anode chamber of the third diaphragm electrolytic cell; wherein:
electrolysis in the anode compartment of a first diaphragm electrolysis cellIs VO in nature2+The electrolyte in the cathode chamber is V3+Acid of (2)
A solution;
the electrolyte in the anode chamber of the second diaphragm electrolytic cell is acidic electrolyte, and the electrolyte in the cathode chamber of the second diaphragm electrolytic cell is first diaphragm electrolyte
Electrolyte VO of anode chamber in electrolytic cell2+VO generated by oxidation reaction of acid solution2 +The solution and electrolyte in the cathode chamber of the second diaphragm electrolytic cell are subjected to reduction reaction to generate VO2+The solution is circulated back to the anode chamber of the first diaphragm electrolytic cell, and oxygen is generated in the anode chamber of the second diaphragm electrolytic cell;
the electrolyte in the anode compartment of the third diaphragm cell is derived from the cathode compartment electrolyte V in the first diaphragm cell3+Acid dissolution of
V generated by reduction reaction of liquid2+The solution and electrolyte in the anode chamber of the third diaphragm electrolytic cell are subjected to oxidation reaction to generate V3+The solution is circulated back to the cathode chamber of the first diaphragm electrolytic cell, the electrolyte in the cathode chamber of the third diaphragm electrolytic cell is acidic electrolyte, and hydrogen is generated in the cathode chamber of the third diaphragm electrolytic cell.
2. A device for producing hydrogen by electrolyzing water step by step based on an all-vanadium redox flow medium is characterized by comprising a first diaphragm electrolytic cell for charging and discharging an all-vanadium redox flow battery, a second diaphragm electrolytic cell for producing oxygen and a hydrogen evolution unit for producing hydrogen; the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank; the anode chamber of the first diaphragm electrolytic cell is communicated with the cathode chamber of the second diaphragm electrolytic cell in a bidirectional way, and the cathode chamber of the first diaphragm electrolytic cell is communicated with the chemical catalytic solid-liquid reaction tank in a bidirectional way; wherein:
the electrolyte in the anode chamber of the first diaphragm electrolytic cell is VO2+The electrolyte in the cathode chamber is V3+Acid of (2)
A solution;
the electrolyte in the anode chamber of the second diaphragm electrolytic cell is acidic electrolyte, and the electrolyte in the cathode chamber of the second diaphragm electrolytic cell is first diaphragm electrolyte
Electrolyte VO of anode chamber in electrolytic cell2+VO generated by oxidation reaction of acid solution2 +The solution and electrolyte in the cathode chamber of the second diaphragm electrolytic cell are subjected to reduction reaction to generate VO2+The solution is circulated back to the anode chamber of the first diaphragm electrolytic cell, and oxygen is generated in the anode chamber of the second diaphragm electrolytic cell;
the reaction solution in the chemical catalysis solid-liquid reaction tank is derived from the electrolyte V in the cathode chamber in the first diaphragm electrolytic tank3+V generated by reduction reaction of acid solution2+Adding a hydrogen evolution catalyst into the chemical catalysis solid-liquid reaction tank to catalyze the solid-liquid chemical reaction, circulating the reaction solution after the reaction back to the cathode chamber of the first diaphragm electrolytic tank, and generating hydrogen in the chemical catalysis solid-liquid reaction tank.
3. The device for producing hydrogen through water electrolysis in steps based on the all-vanadium redox flow medium is characterized in that the electrolyte in the anode chamber in the second diaphragm electrolytic cell and the electrolyte in the cathode chamber in the third diaphragm electrolytic cell are respectively sulfuric acid, phosphoric acid, methanesulfonic acid or perchloric acid, and the concentration of the electrolyte in the anode chamber and the electrolyte in the cathode chamber is 1-5 mol/L, preferably 3 mol/L;
the supporting electrolyte in the first diaphragm electrolytic cell is sulfuric acid, hydrochloric acid, phosphoric acid or methane sulfonic acid, and the concentration is 1-5 mol/L;
the electrolyte of the cathode chamber in the first diaphragm electrolytic cell is vanadium sulfate V2(SO4)3The concentration is 0.5-3 mol/L;
the electrolyte of the anode chamber in the first diaphragm electrolytic cell is vanadyl sulfate VOSO4The concentration is 0.5 to 3 mol/mol.
4. The apparatus for fractional electrolysis of water to produce hydrogen based on an all vanadium redox flow media according to claim 1 or 2 wherein the membranes of the first, second and third membrane cells are independently selected from one of Nafion, PBI, SPEEK or PAN porous membranes.
5. The device for producing hydrogen by stepwise electrolysis of water based on the all-vanadium redox flow media is characterized in that the anode and the cathode in the first diaphragm electrolyzer are independently selected from one of graphite felt, carbon paper or carbon cloth; the cathode in the second diaphragm electrolytic cell is selected from one of graphite felt, carbon paper or carbon cloth, and the anode is an oxygen evolution catalytic electrode; the anode in the third diaphragm electrolytic cell is selected from one of graphite felt, carbon paper or carbon cloth, and the cathode is a hydrogen evolution catalytic electrode.
6. The all-vanadium liquid flow redox medium-based device for producing hydrogen by stepwise electrolysis of water according to claim 5, wherein the electrode materials of the oxygen evolution catalytic electrode are as follows:
based on Ru, Ir or Pt noble metals, alloys and compounds; or
Based on the simple substances or compounds of transition metals of Ni, Co, Fe or Mn; or
N, S, P doped carbon; or
A bioelectrochemical catalyst, such as laccase.
7. The all-vanadium liquid flow redox medium-based device for producing hydrogen by stepwise electrolysis of water according to claim 5, wherein the electrode materials of the hydrogen evolution catalytic electrode are as follows:
based on Pt, Pd, Au or Ag and their complexes with carbon; or
A simple substance or compound based on a transition metal of Ni, Co, or Fe; or
A Cu-based compound; or
A W-based compound; or
A Mo-based compound; or
C3N4A compound is provided.
8. The all-vanadium liquid flow redox medium-based device for producing hydrogen by stepwise electrolysis of water according to claim 2, wherein the hydrogen evolution catalyst is
Based on Pt, Pd, Au or Ag and their complexes with carbon; or
A simple substance or compound based on a transition metal of Ni, Co, or Fe; or
A Cu-based compound; or
A W-based compound; or
A Mo-based compound; or
C3N4A compound is provided.
9. The apparatus for fractional electrolysis of water to produce hydrogen based on an all vanadium redox flow media of claim 1 or 2, wherein the hydrogen evolution unit is a third diaphragm electrolyzer, the apparatus further comprises 4 storage acid V2(SO4)3Electrolyte, acidic VOSO4The storage tanks are respectively communicated with the anode chamber of the first diaphragm electrolytic cell and the cathode chamber of the second diaphragm electrolytic cell, the cathode chamber of the first diaphragm electrolytic cell and the anode chamber of the third diaphragm electrolytic cell, the anode chamber of the second diaphragm electrolytic cell and the cathode chamber of the third diaphragm electrolytic cell, and the storage tanks and the diaphragm electrolytic cells are circulated through a pump;
when the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank, the device also comprises 3 acid storage V2(SO4)3Electrolyte, acidic VOSO4The storage tanks are respectively communicated with the anode chamber of the first diaphragm electrolytic cell, the cathode chamber of the second diaphragm electrolytic cell, the cathode chamber of the first diaphragm electrolytic cell, the chemical catalytic solid-liquid reaction cell and the anode chamber of the second diaphragm electrolytic cell; the storage tank and the diaphragm electrolytic cell are circulated by a pump.
10. An operation method of the device for producing hydrogen by stepwise electrolysis of water based on the redox medium of the all-vanadium liquid flow according to claim 1 or 2, is characterized by comprising the following specific steps:
when the first hydrogen evolution unit is a third diaphragm electrolytic cell
Charging an all-vanadium redox flow battery in a first diaphragm electrolytic cell:
v of cathode chamber in first diaphragm electrolytic cell3+Is electrochemically reduced to V2+VO of the anode compartment2+Is electrochemically oxidized into VO2 +(ii) a In the process, electrons are guided to the cathode from the anode through an external circuit, and meanwhile, hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm; subsequently, the electrolyte in the anode chamber of the first diaphragm electrolytic cell is circulated to the cathode chamber of the second diaphragm electrolytic cell, and the electrolyte in the cathode chamber of the first diaphragm electrolytic cell is circulated to the anode chamber of the third diaphragm electrolytic cell;
(II) electrolyzing the hydrogen and oxygen in the second diaphragm electrolytic cell and the third diaphragm electrolytic cell:
VO of cathode chamber in second diaphragm electrolytic cell2 +Is electrochemically reduced into VO2+Water is electrochemically oxidized into oxygen on the surface of the anode chamber oxygen evolution catalytic electrode; in the process, electrons are guided to the cathode by the anode through an external circuit, and meanwhile, hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm; subsequently the electrolyte in the cathode compartment of the second diaphragm cell is recycled to the anode compartment of the first diaphragm cell;
in the third diaphragm electrolytic cell, the anode chamber is electrochemically oxidized to form hydrogen ions on the surface of the hydrogen evolution catalytic electrode in the cathode chamber
Is electrochemically reduced to hydrogen; in the process, electrons are guided to the cathode by the anode through an external circuit, and meanwhile, hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm; subsequently the electrolyte in the anode compartment of the third diaphragm electrolytic cell is recycled to the cathode compartment of the first diaphragm electrolytic cell;
the electrolysis processes of the second diaphragm electrolytic cell and the third diaphragm electrolytic cell are carried out at different times or simultaneously;
the step (one) and the step (two) are alternately carried out;
when the hydrogen evolution unit is a chemical catalysis solid-liquid reaction tank
Charging an all-vanadium redox flow battery in a first diaphragm electrolytic cell:
v of cathode chamber in first diaphragm electrolytic cell3+Is electrochemically reduced to V2+VO of the anode compartment2+Is electrochemically implemented
Oxidation to VO2 +(ii) a In the process, electrons are guided to the cathode from the anode through an external circuit, and meanwhile, hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm; then firstElectrolyte in the anode chamber of the diaphragm electrolytic cell is circulated to the cathode chamber of the second diaphragm electrolytic cell, and electrolyte in the cathode chamber of the first diaphragm electrolytic cell is circulated to the chemical catalytic solid-liquid reaction tank;
(II) oxygen generation by electrolysis in a second diaphragm electrolytic cell and hydrogen generation by catalysis in a chemical catalysis solid-liquid reaction tank:
VO of cathode chamber in second diaphragm electrolytic cell2 +Is electrochemically reduced into VO2+Water in anode chamber oxygen evolution catalytic electricity
The electrode surface is electrochemically oxidized to oxygen; in the process, electrons are guided to the cathode by the anode through an external circuit, and meanwhile, hydrogen ions generated in the anode chamber are diffused to the cathode chamber through the diaphragm; subsequently the electrolyte in the cathode compartment of the second diaphragm cell is recycled to the anode compartment of the first diaphragm cell;
in the chemical catalysis solid-liquid reaction tank, hydrogen ions are catalytically reduced to hydrogen gas V on the hydrogen evolution catalyst2+Is catalyzed by
Oxidation to V3+(ii) a Then the solution in the chemical catalysis solid-liquid reaction tank is circulated to the cathode chamber of the first diaphragm electrolytic tank;
the electrolysis process of the second diaphragm electrolytic cell and the chemical catalysis process of the chemical catalysis solid-liquid reaction cell are carried out at different times or
Simultaneously carrying out the steps;
the step (one) and the step (two) are alternately carried out.
CN202110596737.4A 2021-05-31 2021-05-31 Device and method for producing hydrogen by electrolyzing water step by step based on all-vanadium liquid flow redox medium Pending CN113416972A (en)

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