CN114457351A - Method and device for producing hydrogen by electrolyzing water step by step based on single-electrolytic-tank double-electrode two-step method - Google Patents
Method and device for producing hydrogen by electrolyzing water step by step based on single-electrolytic-tank double-electrode two-step method Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 128
- 239000001257 hydrogen Substances 0.000 title claims abstract description 128
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 98
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000001301 oxygen Substances 0.000 claims abstract description 96
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910002640 NiOOH Inorganic materials 0.000 claims abstract description 8
- -1 hydroxide ions Chemical class 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000007772 electrode material Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910017299 Mo—O Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 108010029541 Laccase Proteins 0.000 claims description 2
- 229910017313 Mo—Co Inorganic materials 0.000 claims description 2
- 229910018104 Ni-P Inorganic materials 0.000 claims description 2
- 229910018536 Ni—P Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 15
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 8
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 8
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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 a single electrolytic cell and double electrodes. The device comprises an electrolytic bath, and a hydrogen and oxygen evolution dual-function electrode and a nickel hydroxide electrode which are arranged in the electrolytic bath. The hydrogen production process comprises two steps: electrolytic production of hydrogen comprising H2O is electrochemically reduced on the surface of the hydrogen evolution and oxygen evolution double-function electrode to generate hydrogen, and simultaneously Ni (OH)2The electrode is electrochemically oxidized to NiOOH; electrolytic oxygen generation comprising electrochemical reduction of NiOOH electrodes to Ni (OH)2Meanwhile, hydroxide ions are electrochemically oxidized into oxygen on the surface of the hydrogen evolution and oxygen evolution dual-function electrode; two are providedThe steps can be circularly and alternately carried out. Compared with the traditional hydrogen production by acid electrolysis of water, the method can greatly reduce the electrolysis cost. Meanwhile, the structure of the single electrolytic cell is convenient to operate and is connected in series and parallel in actual production, the scale is easy to enlarge, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to a method and a device for producing hydrogen by electrolyzing water step by step based on a single electrolytic cell and double electrodes in a two-step method.
Background
Energy is an important guarantee for the operation of the human society at present. Since the second industrial revolution, the wide use of fossil energy such as coal, oil and natural gas has greatly promoted social development and improved quality of life of people, but has brought a series of problems such as greenhouse effect and air-sea land pollution. Meanwhile, China is used as an import country of petroleum and natural gas, and the development is restricted by energy export countries. Under the background of carbon neutralization and the rapid development of the state, the search for low-carbon energy with wide and reliable sources becomes an important subject.
At present, the capacity of water and electricity tends to be saturated, and people turn the attention to clean renewable energy sources such as wind power, photoelectricity and the like. However, the two kinds of energy are restricted by environment, the power generation is unstable, and the direct grid connection is easy to damage the power grid. The electrolysis of water to produce hydrogen is an important means to solve this problem. The hydrogen has small density and large specific energy, and only generates water in the combustion process, thereby not causing any pollution to the environment and being a good medium for storing energy. The raw material source of the electrolyzed water is very wide, and the electrolyzed water can be almost carried out at any time and any place. Therefore, the electrolysis of water to produce hydrogen is increasingly gaining attention.
The alkaline electrolytic water technology is developed earliest, is mature in industrialization and is most widely applied. However, hydrogen and oxygen are simultaneously generated during electrolysis, mixing easily occurs, it is difficult to directly obtain hydrogen with higher purity, and additional purification cost is often required. Acidic electrolyzed waters based on proton exchange membranes were subsequently developed, the presence of which could isolate the anode and cathode. Then the kinetics of electrochemical hydrogen evolution and oxygen evolution are different, so that the pressure difference exists between two sides of the membrane, the membrane is easy to damage, and the service life of the device is shortened. Meanwhile, the price of the proton exchange membrane (such as a Nafion membrane) with good performance is higher at present, and the cost of the electrolyzed water is increased. The existence of the proton exchange membrane also increases the internal resistance of the electrolytic cell, so that the energy consumption of the electrolyzed water is increased and the energy efficiency is reduced.
Aiming at the problems, a method and a device for producing hydrogen by electrolyzing water based on a three-electrode system through a two-step method (patent application number: 201510799110.3) and a device and a method for producing hydrogen by electrolyzing water based on a three-electrode system and a double-electrolytic-tank two-step method (patent application number: 201610164054.0) are invented, so that the separation of hydrogen production and oxygen production steps in time is realized, and pure hydrogen and pure oxygen are prepared by alkaline electrolyzed water without a diaphragm. However, both of these methods are based on a three-electrode system, and switching of the electrodes connected to an external circuit is required between the hydrogen production and oxygen production steps, which increases the complexity of the electrolysis operation and reduces the feasibility. Meanwhile, frequent electrode switching is not beneficial to series-parallel integration of the electrolytic cell and large-scale industrial preparation of pure hydrogen.
Disclosure of Invention
The invention aims to overcome the difficulty of water electrolysis and provides a method and a device for producing hydrogen by water electrolysis step by step based on a single-electrolytic-cell double-electrode two-step method, which have high hydrogen production purity and low cost and are easy to realize series-parallel integration.
The device for producing hydrogen by water electrolysis step by step based on a single-electrolytic-tank double-electrode two-step method comprises an electrolytic tank, and a hydrogen-evolution and oxygen-evolution double-function electrode and a nickel hydroxide electrode which are arranged in the electrolytic tank.
In the invention, the hydrogen evolution and oxygen evolution dual-function electrode can catalyze electrolysis of water to generate hydrogen and can also catalyze electrolysis of water, and the electrode material with the catalytic action can be a hydrogen evolution and oxygen evolution dual-function material and can also be a composite material of the hydrogen evolution electrode material and the oxygen evolution electrode material.
In the invention, the hydrogen evolution and oxygen evolution dual-function material has a catalytic effect on hydrogen and oxygen generated by electrolyzing water. Specifically, the electrode material with the catalytic action is as follows:
a Pt electrode; or
A Cu-Co-Mo-O based compound; or
A Ni-Co-Mo-S based compound; or
A Ni-P based compound; or
A Co-P based compound; or
A Ni-Mo-Co based metal compound; or
A FeP compound; or
N, P, O, S doped carbon material.
In the invention, the hydrogen evolution electrode material has a catalytic action on the generation of hydrogen by electrolyzing water, and the electrode material with the catalytic action is as follows:
based on metallic platinum and its complexes with carbon; or
Simple substances or compounds based on transition metals of Ni, Co or Fe; or
A Cu-based compound; or
A W-based compound; or
A Mo-based compound; or
C3N4 A compound is provided.
In the invention, the hydrogen evolution electrode material has a catalytic action on the generation of oxygen by electrolyzing water, and the electrode material with the catalytic action is as follows:
compounds based on Ru or Ir noble metals; or
Based on the simple substances or compounds of transition metals of Ni, Co, Fe or Mn; or
N, S, P doped carbon; or
Laccase, and other bioelectrochemical catalysts.
In the present invention, the nickel hydroxide electrode is made of Ni (OH)2Active material and other additive components, wherein the additive components are silver powder, Co (OH)2One or more of carbon powder and adhesive.
In the present invention, the Ni (OH) 2The active substance and the additive components are pressed or coated on the metal current collector to form Ni (OH) by a mode of mixing into a film or forming into slurry 2An electrode; the metal current collector includes: nickel mesh, nickel foam, stainless steel mesh or titanium mesh.
In the invention, the electrolyte of the water electrolysis technology is an alkaline aqueous solution, and the solute of the alkaline aqueous solution is potassium hydroxide or sodium hydroxide.
In the invention, the device is used as an electrolytic water unit, and a plurality of units can pass different units of Ni (OH)2The electrodes are connected in series with the hydrogen evolution and oxygen evolution double-function electrodes, and can also be connected in series through different units of Ni (OH)2The electrodes are connected in parallel and the hydrogen and oxygen evolution dual-function electrodes are connected in parallel.
The invention further provides a single-electrolytic-cell double-electrode two-step water electrolysis hydrogen production method based on the device, which comprises the following specific steps:
hydrogen production by electrolysis:
in the electrolytic cell, H2Hydrogen and oxygen evolution double-function electrode with O as cathodeIs electrochemically reduced to H2I.e. 2H2O+ 2e-→ H2↑+OH-(ii) a Ni (OH) as anode at the same time2The electrode is electrochemically oxidized to a NiOOH electrode, i.e. Ni (OH)2+ OH- - e-→NiOOH + H2O; the electrons in this process are composed of Ni (OH)2The electrode flows to the hydrogen evolution and oxygen evolution dual-function electrode through an external circuit;
(II) oxygen generation by electrolysis:
in the electrolytic tank, the NiOOH electrode as the cathode is electrochemically reduced to Ni (OH)2Electrodes, i.e. NiOOH + H2O + e-→ Ni(OH)2 + OH-(ii) a With OH-Electrochemically oxidized to O on the surface of a hydrogen-evolving and oxygen-evolving bifunctional electrode as anode2I.e. 4OH-- 4e-→2H2O + O2×) ×; in the process, electrons flow from the hydrogen evolution and oxygen evolution dual-function electrode to the NiOOH electrode through an external circuit.
The step (I) and the step (II) are alternately carried out to realize the preparation of pure hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
the most remarkable characteristic of the single-electrolytic-cell-based double-electrode two-step water electrolysis hydrogen production is that Ni (OH) is utilized2NiOOH is used as an oxidation-reduction medium to decompose the electrolyzed water into two steps, so that the separation of hydrogen production and oxygen production in time is realized, and pure hydrogen can be obtained without a diaphragm. In addition, by using the hydrogen and oxygen evolution dual-function electrode, the step electrolysis can be realized on the two electrodes, the electrodes do not need to be switched between the hydrogen production and the oxygen production, and the operation complexity can be reduced. And the electrolytic cells can be conveniently integrated in series and parallel connection so as to realize the industrial large-scale step-by-step hydrogen production by water electrolysis.
Compared with the traditional hydrogen production by acid electrolysis of water, the method does not involve the simultaneous production of hydrogen and oxygen, does not need an ion exchange membrane to separate two electrodes, directly generates high-purity hydrogen, and greatly reduces the electrolysis cost. Meanwhile, the structure of the single electrolytic cell is convenient to operate and is connected in series and parallel in actual production, the scale is easy to enlarge, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of a device and a method for producing hydrogen by water electrolysis step by step based on a single-electrolytic-tank double-electrode two-step method.
FIG. 2 is an electrolysis curve of water-step electrolysis hydrogen production based on a single-electrolytic-cell double-electrode two-step method.
FIG. 3 is a schematic view of three electrolytic cells connected in series.
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 hydrogen evolution and oxygen evolution dual-function electrode adopts a CoP @ N doped graphene electrode, and the nickel hydroxide electrode adopts a commercial nickel hydroxide electrode purchased from the market. All electrodes were 20 cm square. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.58V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.52V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (FIG. 2) (see Table 1).
Example 2
Co is adopted as the hydrogen evolution and oxygen evolution double-function electrode3O4@ graphene, a commercially available nickel hydroxide electrode was used as the nickel hydroxide electrode. All electrodes were 20 cm square. The electrolyte adopts 500 ml of 1 mol/L potassium hydroxide solution, adopts 200 milliamperes constant current and uses blue with 2A measuring rangeThe electric cell testing device performs constant current electrolysis. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.65V. At this time, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.67V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 3
The hydrogen evolution and oxygen evolution dual-function electrode adopts MoS2@Ni3S2The nickel hydroxide electrode is a commercially available nickel hydroxide electrode. All electrodes were 20 cm square. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A-range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.55V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.51V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 4
The hydrogen evolution and oxygen evolution dual-function electrode adopts a Cu-Co-Mo-O compound, and the nickel hydroxide electrode adopts a commercial nickel hydroxide electrode purchased in the market. All electricityThe poles are all 20 square centimeters. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.60V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.54V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 5
The hydrogen evolution and oxygen evolution double-function electrode adopts FeP @ graphene, and the nickel hydroxide electrode adopts Ni (OH) purchased in the market2@ carbon nanotubes. All electrodes were 20 cm square. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.63V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.58V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 6
Hydrogen and oxygen evolution double-function electrodeBy C3N4@ graphene composite IrO2The nickel hydroxide electrode is a commercially available nickel hydroxide electrode. All electrodes were 20 cm square. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A-range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.59V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, the voltage rises to 1.0V at the end, and the average voltage is 0.53V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 7
The hydrogen evolution and oxygen evolution double-function electrode adopts MoS2@ graphene composite IrO2The nickel hydroxide electrode is a commercially available nickel hydroxide electrode. All electrodes were 20 cm square. The electrolyte is prepared from 500 ml of 1 mol/L potassium hydroxide solution, and is subjected to constant current electrolysis by using a 2A range blue battery testing device under the constant current of 200 milliamperes. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 1.60V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, and the voltage rises to 1.0V at the end, and the average voltage is 0.51V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. Gas mass spectrum is respectively used in the process of collecting two gasesIt was identified that no mixing of hydrogen and oxygen occurred. (see Table 1).
Example 8
The hydrogen evolution and oxygen evolution double-function electrode adopts MoS2@Ni3S2The nickel hydroxide electrode is a commercially available nickel hydroxide electrode. All electrodes were 20 cm square. Three series integration is carried out on 3 electrolytic tanks according to the mode shown in figure 3, the electrolyte adopts 500 ml of 1 mol/L potassium hydroxide solution, constant current of 200 milliampere is adopted, and a blue battery testing device with 2A measuring range is used for carrying out constant current electrolysis. Firstly, the cathode is connected with a hydrogen evolution and oxygen evolution double-function electrode, and the anode is connected with nickel hydroxide (Ni (OH)2) The electrodes were charged with 200 milliamps of current for 600 seconds at an average voltage of 4.70V. At the moment, hydrogen is generated and collected on the hydrogen evolution and oxygen evolution double-function electrode, Ni (OH)2The electrode was oxidized to a nickel oxyhydroxide (NiOOH) electrode. Then the cathode is connected with a NiOOH electrode, the anode is connected with a hydrogen and oxygen evolution dual-function electrode, 200 milliamperes of current is applied for 600 seconds, the voltage rises to 3.0V at the end, and the average voltage is 1.60V. At the moment, oxygen is generated and collected on the hydrogen evolution and oxygen evolution dual-function electrode, and the NiOOH electrode is reduced into Ni (OH)2And an electrode. The two gases were collected and identified separately by gas mass spectrometry, confirming that no mixing of hydrogen and oxygen occurred. (see Table 1).
TABLE 1 comparison of 200 mA constant current electrolytic water performances of an electrolytic cell adopting different electrode assembly and connection modes
Claims (10)
1. A device for producing hydrogen by water electrolysis step by step based on a single electrolytic cell and double electrodes two-step method is characterized by comprising an electrolytic cell, and a hydrogen evolution and oxygen evolution double-function electrode and a nickel hydroxide electrode which are arranged in the electrolytic cell;
the hydrogen evolution and oxygen evolution dual-function electrode can catalyze electrolyzed water to generate hydrogen and can also catalyze electrolyzed water; the electrode material with the catalytic action is a hydrogen evolution and oxygen evolution double-function material or a composite material of the hydrogen evolution electrode material and the oxygen evolution electrode material.
2. The apparatus of claim 1, wherein the hydrogen evolution and oxygen evolution dual-function material has a catalytic effect on the generation of both hydrogen and oxygen from the electrolyzed water, and the electrode material with the catalytic effect is:
pt; or
A Cu-Co-Mo-O based compound; or
A Ni-Co-Mo-S based compound; or
A Ni-P based compound; or
A Co-P based compound; or
A Ni-Mo-Co based metal compound; or
A FeP compound; or
N, P, O, S doped carbon material.
3. The apparatus of claim 1, wherein the hydrogen evolution electrode material is catalytic for the electrolysis of water to produce hydrogen gas, and the catalytic electrode material is:
based on metallic platinum and its complexes with carbon; or
Simple substances or compounds based on transition metals of Ni, Co or Fe; or
A Cu-based compound; or
A W-based compound; or
A Mo-based compound; or
C3N4 A compound is provided.
4. The apparatus of claim 1, wherein the oxygen evolving electrode material catalyzes the electrolysis of water to produce oxygen, and the electrode material having such catalysis is:
compounds based on Ru or Ir noble metals; or
Based on the simple substances or compounds of transition metals of Ni, Co, Fe or Mn; or
N, S, P doped carbon; or
Laccase, and other bioelectrochemical catalysts.
5. The apparatus of claim 1, wherein the nickel hydroxide electrode is made of Ni (OH)2Active material and other additive components, wherein the additive components are silver powder, Co (OH)2One or more of carbon powder and adhesive.
6. The device of claim 5, wherein the binder is polytetrafluoroethylene.
7. The apparatus of claim 5, wherein said Ni (OH) 2The active substance and the additive components are pressed or coated on the metal current collector to form Ni (OH) by a mode of mixing into a film or forming into slurry 2An electrode; the metal current collector includes: nickel mesh, nickel foam, stainless steel mesh or titanium mesh.
8. The apparatus of claim 1, wherein the electrolyte of the electrolytic water technology is an alkaline aqueous solution, and the solute of the alkaline aqueous solution is potassium hydroxide or sodium hydroxide.
9. The apparatus according to any one of claims 1 to 8, wherein the apparatus is used as a water electrolysis unit, and a plurality of units are separated by different units of Ni (OH)2The electrodes are connected in series with the hydrogen evolution and oxygen evolution double-function electrodes or connected in series through different units of Ni (OH)2The electrodes are connected in parallel and the hydrogen and oxygen evolution dual-function electrodes are connected in parallel.
10. A two-step method for producing hydrogen by electrolyzing water based on the device of any of claims 1 to 9, comprising the following steps:
hydrogen production by electrolysis:
in the electrolytic cell, H2O is electrochemically reduced to H on the surface of the hydrogen evolution and oxygen evolution double-function electrode as a cathode2I.e. 2H2O+ 2e-→ H2↑+OH-(ii) a Ni (OH) as an anode at the same time2The electrode is electrochemically oxidized to a NiOOH electrode, i.e. Ni (OH)2 + OH-- e-→NiOOH+ H2O; the electrons in this process are composed of Ni (OH)2The electrode flows to the hydrogen evolution and oxygen evolution dual-function electrode through an external circuit;
(II) oxygen generation by electrolysis:
in the electrolytic tank, the NiOOH electrode as the cathode is electrochemically reduced to Ni (OH)2Electrodes, i.e. NiOOH + H2O + e-→ Ni(OH)2 + OH-(ii) a With OH-Electrochemically oxidized to O on the surface of a hydrogen evolution and oxygen evolution dual-function electrode as an anode2I.e. 4OH-- 4e-→2H2O + O2×) ×; in the process, electrons flow from the hydrogen evolution and oxygen evolution dual-function electrode to the NiOOH electrode through an external circuit;
the step (I) and the step (II) are alternately carried out to realize the preparation of high-purity hydrogen.
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| CN105420748A (en) * | 2015-11-18 | 2016-03-23 | 复旦大学 | Two-step method and device for producing hydrogen through water electrolysis on basis of three-electrode system |
| 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 |
| CN113913844A (en) * | 2021-10-22 | 2022-01-11 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Membrane-free water electrolysis hydrogen production device based on power supply switching |
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| CN105420748A (en) * | 2015-11-18 | 2016-03-23 | 复旦大学 | Two-step method and device for producing hydrogen through water electrolysis on basis of three-electrode system |
| 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 |
| CN113913844A (en) * | 2021-10-22 | 2022-01-11 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Membrane-free water electrolysis hydrogen production device based on power supply switching |
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| CN115094435A (en) * | 2022-06-15 | 2022-09-23 | 中国科学院大连化学物理研究所 | Seawater electrolysis device |
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