CN113913844B - Power switching-based membrane-free water electrolysis hydrogen production device - Google Patents
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Abstract
The invention discloses a power supply switching-based membrane-free water electrolysis hydrogen production device, and relates to the technical field of water electrolysis. Comprises an electrolytic bath, a bipolar electrode and an electrode group, wherein the middle of the electrolytic bath is divided into a left chamber and a right chamber by a nickel plate; alkaline electrolyte is filled in the left chamber and the right chamber; the upper ends of the left chamber and the right chamber are both provided with gas-liquid mixing outlets; the bipolar electrodes are arranged on two sides of the nickel plate, and the two electrode groups are respectively arranged in the left chamber and the right chamber and are connected with the positive/negative electrodes of the electrolysis power supply. According to the invention, the electrode group is respectively connected with the anode and the cathode of the electrolytic power supply in series through the relay, and the circulating hydrogen and oxygen evolution of the electrolytic chamber is realized by switching the anode and the cathode of the electrolytic power supply, so that the hydrogen and oxygen production of the electrolyzed water can be completed in a synchronous chamber circulation manner under the condition of no electrolytic film and high pressure, the hydrogen production of the electrolyzed water is realized with low cost, low energy consumption and stability, the bipolar electrode does not need to be switched, and the sealing problem is solved.
Description
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to a power supply switching-based membrane-free water electrolysis hydrogen production device.
Background
Under the conditions that the total amount of fossil energy is limited and a large amount of pollution emission is generated, hydrogen energy is considered as an important bridge for connecting fossil energy to renewable energy, and a hydrogen source development and hydrogen production link is a first premise for developing hydrogen energy economy. At present, the hydrogen production by reforming fossil fuel is mainly adopted in industry, and the requirements of sustainable development are not met from the viewpoints of environmental protection and energy loss. Compared with the traditional hydrogen production process, the hydrogen production by electrolyzing water has the advantages of wide raw material source, low price, clean preparation process and high product purity; in addition, the electric energy for driving the water decomposition can be converted from new energy sources such as solar energy, wind energy, hydraulic energy, geothermal energy and the like. The conversion between these sustainable energy sources not only can realize the storage of renewable energy sources converted into chemical fuels by electrolyzing water, but also makes up the gap of sustainable supply of energy sources in time and space, so the method is recognized as a green hydrogen production route with the most development prospect.
The conventional water electrolysis hydrogen production must adopt an ion exchange membrane to separate hydrogen and oxygen, the ion exchange membrane is expensive, the cost of hydrogen production by electrolysis is increased, meanwhile, the use of the membrane increases the internal resistance of a system, the energy consumption is improved, and the traditional water electrolysis process needs very stable power input to ensure H 2 And O 2 The yield is balanced and the pressure difference across the membrane is reduced. However, the oxygen evolution process exhibits slower kinetic characteristics compared to the hydrogen evolution process; with the change of input power, the response rate of the hydrogen evolution/oxygen evolution process is different, which inevitably causes the increase of the instant pressure difference at two sides of the membrane, further leads to the danger of membrane damage and gas mixing, and in addition, because of H 2 、O 2 And the presence of an electrolyzed water catalyst, active oxygen is generated, which has a degrading effect on the ion exchange membrane, thereby reducing the service life of the membrane.
In order to solve the technical problem, in recent years, a two-step water electrolysis hydrogen production technology is developed, wherein the two-step method is based on three electrodes: hydrogen evolution electrode, oxygen evolution electrode, foamed nickel and cobalt doped electrode, etc. nickel surface in alkali liquor is anode oxidized to produce Ni (OH) 2 A NiOOH oxide cap layer. The foamed nickel electrode respectively produces hydrogen and oxygen by switching the foamed nickel electrode in an interval insertion mode or a continuous rotation mode, so that the electrolysis process is continuously carried out. This foaming is effectedThe problem with the frequent switching of nickel electrodes is the problem of a complete seal at high pressures.
Disclosure of Invention
The invention aims to provide a power supply switching-based membraneless water electrolysis hydrogen production device, which is characterized in that an electrode group is respectively connected with a relay in series and connected with the positive electrode and the negative electrode of an electrolysis power supply, the circular hydrogen and oxygen evolution of an electrolysis chamber is realized by switching the positive electrode and the negative electrode of the electrolysis power supply, the hydrogen and oxygen production of water electrolysis is realized by synchronously performing chamber circulation under the conditions of no electrolysis membrane and high pressure, the hydrogen production of water electrolysis with low cost, low energy consumption and stability is realized, a bipolar electrode is not required to be switched, and the sealing problem is solved.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a power supply switching-based membraneless water electrolysis hydrogen production device, which comprises an electrolytic bath, wherein the middle of the electrolytic bath is divided into a left chamber and a right chamber by a nickel plate; alkaline electrolyte is filled in the left chamber and the right chamber; the upper ends of the left chamber and the right chamber are provided with a gas-liquid mixing outlet; the bipolar electrodes are arranged on two sides of the nickel plate, and two ends of each bipolar electrode are respectively inserted into the left chamber and the right chamber; an electrode group, two of which are respectively disposed in the left and right chambers; the electrode group of the left chamber is connected with a first relay in series to the anode of an electrolysis power supply; the electrode group of the left chamber is connected with the second relay in series to the negative electrode of the electrolysis power supply; the electrode group of the right chamber is connected with a third relay in series to the negative electrode of the electrolysis power supply; and the electrode group of the right chamber is connected with the fourth relay in series to the anode of the electrolysis power supply.
Furthermore, the electrode group adopts a dual-function electrode or a combined electrode consisting of an oxygen evolution electrode and a hydrogen evolution electrode.
Further, when the electrode group adopts a dual-function electrode;
the upper end of the double-function electrode of the left chamber is connected with a first relay in series to the anode of an electrolytic power supply; the upper end of the double-function electrode of the left chamber is also connected with a second relay in series to the negative electrode of the electrolysis power supply;
the upper end of the double-function electrode of the right chamber is connected with a third relay in series to the negative electrode of the electrolysis power supply; the upper end of the double-function electrode of the right chamber is also connected with a fourth relay in series to the anode of the electrolysis power supply.
Furthermore, when the electrode group adopts a combined electrode consisting of an oxygen evolution electrode and a hydrogen evolution electrode;
the upper end of the oxygen evolution electrode of the left chamber is connected with a first relay in series to the anode of an electrolysis power supply; the upper end of the hydrogen evolution electrode of the left chamber is connected with a second relay in series to the negative electrode of the electrolysis power supply;
the upper end of the hydrogen evolution electrode of the right chamber is connected with a third relay in series to the negative electrode of the electrolysis power supply; the upper end of the oxygen evolution electrode of the right chamber is connected with a fourth relay in series to the anode of the electrolysis power supply.
Further, the bifunctional electrode is made of hydroxides/oxides, chalcogenides, phosphides, borides of transition metals and mixtures thereof.
Furthermore, the bipolar electrode is made of foamed nickel and doped cobalt, and the nickel surface in the alkali liquor is subjected to anodic oxidation to generate Ni (OH) 2 A NiOOH oxide cap layer.
The invention has the following beneficial effects:
according to the invention, the electrode groups are respectively connected with the anode and the cathode of the electrolytic power supply in series through the relays, the circulating hydrogen and oxygen evolution of the electrolytic chamber is realized by switching the anode and the cathode of the electrolytic power supply, the hydrogen and oxygen production of the electrolyzed water can be completed in a synchronous chamber circulation mode under the condition of no electrolytic film and high pressure, the hydrogen production of the electrolyzed water with low cost, low energy consumption and stability can be realized, the bipolar electrodes do not need to be switched, and the sealing problem is solved.
Of course, it is not necessary for any product to practice the invention to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a power switching-based membraneless water electrolysis hydrogen production device adopting a bifunctional electrode;
FIG. 2 is a schematic structural diagram of a power switching-based membraneless water electrolysis hydrogen production device adopting a single-function oxygen/hydrogen evolution electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
Example 1:
referring to fig. 1-2, the invention relates to a power switching-based membrane-free water electrolysis hydrogen production device, which comprises an electrolytic tank, wherein the middle of the electrolytic tank is divided into a left chamber 1 and a right chamber 2 by a nickel plate 3; alkaline electrolyte is filled in the left chamber 1 and the right chamber 2; the upper ends of the left chamber 1 and the right chamber 2 are both provided with a gas-liquid mixing outlet 7;
the bipolar electrodes 4 are arranged on two sides of the nickel plate 3, and the bipolar electrodes 4 are fixed on two sides of the nickel plate 3 through bolts; the two ends of the bipolar electrode 4 are respectively inserted into the left chamber 1 and the right chamber 2; the bipolar electrode 4 is made of foam nickel and doped cobalt, and the nickel surface in the alkali liquor is subjected to anodic oxidation to generate Ni (OH) 2 A NiOOH oxide cap layer;
an electrode group, which are respectively arranged in the left chamber 1 and the right chamber 2; the electrode group of the left chamber 1 is connected in series with a first relay K1 to the anode of an electrolysis power supply 5; the electrode group of the left chamber 1 is connected with the second relay K2 in series to the negative electrode of the electrolysis power supply 5;
the electrode group of the right chamber 2 is connected with a third relay K3 in series to the negative electrode of the electrolysis power supply 5; the electrode group of the right chamber 2 is connected in series with the fourth relay K4 to the positive electrode of the electrolysis power supply 5.
The electrode group adopts a bifunctional electrode 8 or a combined electrode consisting of an oxygen evolution electrode 9 and a hydrogen evolution electrode 10; the material of the dual-function electrode 8 is hydroxide/oxide, chalcogenide, phosphide, boride of transition metal and the mixture thereof;
when the electrode group adopts the double-function electrode 8; the upper end of the double-function electrode 8 of the left chamber 1 is connected with a first relay K1 to the anode of the electrolysis power supply 5 in series; the upper end of the difunctional electrode 8 of the left chamber 1 is also connected in series with a second relay K2 to the cathode of the electrolysis power supply 5; the upper end of the double-function electrode 8 of the right chamber 2 is connected with a third relay K3 in series to the negative electrode of the electrolysis power supply 5; the upper end of the double-function electrode 8 of the right chamber 2 is also connected with a fourth relay K4 in series to the anode of the electrolysis power supply 5.
When the electrode group adopts a combined electrode consisting of an oxygen evolution electrode 9 and a hydrogen evolution electrode 10; the upper end of the oxygen evolution electrode 9 of the left chamber 1 is connected with a first relay K1 in series to the anode of the electrolysis power supply 5; the upper end of the hydrogen evolution electrode 10 of the left chamber 1 is connected with a second relay K2 in series to the cathode of the electrolysis power supply 5; the upper end of the hydrogen evolution electrode 10 of the right chamber 2 is connected with a third relay K3 in series to the negative electrode of the electrolysis power supply 5; the upper end of the oxygen evolution electrode 9 of the right chamber 2 is connected in series with a fourth relay K4 to the anode of the electrolysis power supply 5.
Example 2: based on example 1;
as shown in fig. 1, in the present embodiment, the electrode group employs a dual function electrode 8;
the hydrogen production process is as follows: firstly, closing K1 and K3, and disconnecting K2 and K4; at this time, the process of the present invention,
in the right chamber 2:
water molecules are electrochemically reduced to hydrogen, i.e. H, at the surface of the bifunctional electrode 8 as cathode 2 O+e-→1/2H 2 +OH - (ii) a Ni (OH) as anode at the same time 2 The electrode is electrochemically oxidized to NiOOH electrodes, i.e. Ni (OH) 2 +OH - －e-→NiOOH+H 2 O；
In the left compartment 1:
the NiOOH electrode as cathode is electrochemically reduced to Ni (OH) 2 Electrodes, i.e. NiOOH + H 2 O+e-→Ni(OH) 2 +OH - (ii) a At the same time, the hydroxide ions are electrochemically oxidized to oxygen, i.e. 2OH, on the surface of the bifunctional electrode 8 as anode - －2e-→1/2O 2 +H 2 O；
According to the power supply pressure rising threshold or the hydrogen production speed falling threshold required by constant current electrolytic water, the capacitance saturation of the bipolar electrode 4 is represented at the moment; cutting off K1 and K3, and suspending hydrogen production and oxygen production; discharging hydrogen and oxygen in the left chamber 1 and the right chamber 2 by adding alkali liquor into the left chamber 1 and the right chamber 2;
closing K2 and K4 after the hydrogen and oxygen collecting ports cannot detect the hydrogen and oxygen; at this time, the process of the present invention,
in the left compartment 1:
water molecules are electrochemically reduced to hydrogen, i.e., H, at the surface of the bifunctional electrode 8 as a cathode 2 O+e-→1/2H 2 +OH - (ii) a Ni (OH) as anode at the same time 2 The electrode is electrochemically oxidized to a NiOOH electrode, i.e. Ni (OH) 2 +OH - －e-→NiOOH+H 2 O；
In the right chamber 2:
the NiOOH electrode as cathode is electrochemically reduced to Ni (OH) 2 Electrodes, i.e. NiOOH + H 2 O+e-→Ni(OH) 2 +OH - (ii) a At the same time, the hydroxide ions are electrochemically oxidized to oxygen, i.e. 2OH, on the surface of the bifunctional electrode 8 as anode - －2e-→1/2O 2 +H 2 O；
According to the power supply pressure rising threshold or hydrogen production speed falling threshold required by constant current electrolytic water, the capacitance of the bipolar electrode 4 is saturated at the moment; cutting off K2 and K4, and suspending hydrogen production and oxygen production; discharging hydrogen and oxygen in the left chamber 1 and the right chamber 2 by adding alkali liquor into the left chamber 1 and the right chamber 2;
closing K1 and K3 after the hydrogen and oxygen collecting ports can not detect the hydrogen and oxygen; so as to circularly produce hydrogen and oxygen.
Example 3: based on example 1;
as shown in fig. 2, in the present embodiment, the electrode group employs a combined electrode composed of an oxygen evolution electrode 9 and a hydrogen evolution electrode 10;
the hydrogen production process is as follows: firstly, closing K1 and K3, and disconnecting K2 and K4; the oxygen evolution electrode 9 of the left chamber 1 is connected with the anode of the electrolysis power supply 5, and the hydrogen evolution electrode 10 of the right chamber 2 is connected with the cathode of the electrolysis power supply 5; at this time, the process of the present invention,
in the right chamber 2:
water molecules are electrochemically reduced to hydrogen gas, i.e., H, on the surface of the hydrogen evolution electrode 10 serving as a cathode 2 O+e-→1/2H 2 +OH - (ii) a Ni (OH) as anode at the same time 2 The electrode is electrochemically oxidized to a NiOOH electrode, i.e. Ni (OH) 2 +OH - －e-→NiOOH+H 2 O；
In the left ventricle 1:
the NiOOH electrode as cathode is electrochemically reduced to Ni (OH) 2 Electrodes, i.e. NiOOH + H 2 O+e-→Ni(OH) 2 +OH - (ii) a At the same time, the hydroxide ions are electrochemically oxidized into oxygen, i.e. 2OH, on the surface of the oxygen evolution electrode 9 as an anode - －2e-→1/2O 2 +H 2 O；
According to the power supply pressure rising threshold or the hydrogen production speed falling threshold required by constant current electrolytic water, the capacitance saturation of the bipolar electrode 4 is represented at the moment; cutting off K1 and K3, and suspending hydrogen production and oxygen production; discharging hydrogen and oxygen in the left chamber 1 and the right chamber 2 by adding alkali liquor into the left chamber 1 and the right chamber 2;
closing K2 and K4 after the hydrogen and oxygen collecting ports cannot detect the hydrogen and oxygen; the hydrogen evolution electrode 10 of the left chamber 1 is connected with the cathode of the electrolysis power supply 5, and the oxygen evolution electrode 9 of the right chamber 2 is connected with the anode of the electrolysis power supply 5; at this time, the process of the present invention,
in the left ventricle 1:
water molecules are electrochemically reduced to hydrogen gas, i.e., H, on the surface of the hydrogen evolution electrode 10 as a cathode 2 O+e-→1/2H 2 +OH - (ii) a Ni (OH) as anode at the same time 2 The electrode is electrochemically oxidized to a NiOOH electrode, i.e. Ni (OH) 2 +OH - －e-→NiOOH+H 2 O；
In the right chamber 2:
the NiOOH electrode as cathode is electrochemically reduced to Ni (OH) 2 Electrodes, i.e. NiOOH + H 2 O+e-→Ni(OH) 2 +OH - (ii) a At the same time, the hydroxide ions are electrochemically oxidized into oxygen, i.e. 2OH, on the surface of the oxygen evolution electrode 9 as an anode - －2e-→1/2O 2 +H 2 O；
According to the power supply pressure rising threshold or hydrogen production speed falling threshold required by constant current electrolytic water, the capacitance of the bipolar electrode 4 is saturated at the moment; cutting off K2 and K4, and suspending hydrogen production and oxygen production; discharging hydrogen and oxygen in the left chamber 1 and the right chamber 2 by adding alkali liquor into the left chamber 1 and the right chamber 2;
closing K1 and K3 after the hydrogen and oxygen collecting ports can not detect the hydrogen and oxygen; so as to circularly produce hydrogen and oxygen.
Example 4: based on examples 1-3;
as shown in fig. 1-2, the gas-liquid mixing outlets 6 on the left chamber 1 and the right chamber 2 are respectively connected with two gas-liquid separation tanks for separating and collecting hydrogen and oxygen; a liquid outlet of the gas-liquid separation tank is connected with a circulating pipeline; the liquid separated from the gas is conveyed back to the electrolytic cell through the alkali liquor inlet 6 by the circulating pipeline; the gas-liquid separation tank, the oxygen collector and the hydrogen collector are connected with a flow sensor for detecting gas flow, and the flow sensor is connected with the processor. Detecting the flow of the gas through a flow sensor to judge the electrolysis speed;
Example 5: based on examples 1-3;
the bottoms of the left chamber 1 and the right chamber 2 are respectively provided with an alkali liquor inlet 6, the alkali liquor inlet 6 is connected with a liquor inlet system, the liquor inlet system comprises a liquor inlet pump communicated with the alkali liquor inlet 6, and the liquor inlet pump is arranged in an alkali liquor tank.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The utility model provides a no membrane electrolysis water hydrogen plant based on power switches which characterized in that: comprises that
The middle of the electrolytic cell is divided into a left chamber (1) and a right chamber (2) by a nickel plate (3); alkaline electrolyte is filled in the left chamber (1) and the right chamber (2); the upper ends of the left chamber (1) and the right chamber (2) are respectively provided with a gas-liquid mixing outlet (7);
the bipolar electrodes (4) are arranged on two sides of the nickel plate (3), and two ends of each bipolar electrode (4) are respectively inserted into the left chamber (1) and the right chamber (2);
an electrode group, which is respectively arranged in the left chamber (1) and the right chamber (2); the electrode group of the left chamber (1) is connected with a first relay (K1) in series to the anode of an electrolysis power supply (5); the electrode group of the left chamber (1) is connected with a second relay (K2) in series to the negative electrode of the electrolysis power supply (5);
the electrode group of the right chamber (2) is connected with a third relay (K3) in series to the negative electrode of the electrolysis power supply (5); and the electrode group of the right chamber (2) is connected in series with a fourth relay (K4) to the anode of the electrolysis power supply (5).
2. The power switching-based membraneless electrolytic water hydrogen production device according to claim 1, wherein the electrode group adopts a bifunctional electrode (8) or a combined electrode consisting of an oxygen evolution electrode (9) and a hydrogen evolution electrode (10).
3. The power switching-based membraneless electrolytic water hydrogen production device according to claim 2, wherein when the electrode group adopts the bifunctional electrode (8);
the upper end of the difunctional electrode (8) of the left chamber (1) is connected with a first relay (K1) in series to the anode of the electrolysis power supply (5); the upper end of the difunctional electrode (8) of the left chamber (1) is also connected in series with a second relay (K2) to the negative electrode of the electrolysis power supply (5);
the upper end of the difunctional electrode (8) of the right chamber (2) is connected with a third relay (K3) in series to the negative electrode of the electrolysis power supply (5); the upper end of the double-function electrode (8) of the right chamber (2) is also connected with a fourth relay (K4) in series to the anode of the electrolysis power supply (5).
4. The power supply switching-based membraneless electrolytic water hydrogen production device according to claim 2, wherein when the electrode group adopts a combined electrode consisting of one oxygen evolution electrode (9) and one hydrogen evolution electrode (10);
the upper end of the oxygen evolution electrode (9) of the left chamber (1) is connected with a first relay (K1) in series to the anode of the electrolysis power supply (5); the upper end of the hydrogen evolution electrode (10) of the left chamber (1) is connected with a second relay (K2) in series to the negative electrode of the electrolysis power supply (5);
the upper end of the hydrogen evolution electrode (10) of the right chamber (2) is connected with a third relay (K3) in series to the negative electrode of the electrolysis power supply (5); the upper end of the oxygen evolution electrode (9) of the right chamber (2) is connected with a fourth relay (K4) in series to the anode of the electrolysis power supply (5).
5. The power switching-based membraneless electrolytic water hydrogen production device according to claim 2, wherein the material of the bifunctional electrode (8) is transition metal hydroxide/oxide, chalcogenide, phosphide, boride and their mixture.
6. The power switching-based membraneless water electrolysis hydrogen production device according to claim 1, wherein the bipolar electrode (4) is made of foamed nickel and doped cobalt, and the nickel surface in the alkaline solution is subjected to anodic oxidation to generate Ni (OH) 2 A NiOOH oxide cap layer.
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| CN114457351A (en) * | 2022-02-23 | 2022-05-10 | 复旦大学 | Method and device for producing hydrogen by electrolyzing water step by step based on single-electrolytic-tank double-electrode two-step method |
| CN114457352B (en) * | 2022-02-23 | 2023-11-24 | 复旦大学 | Device and method for hydrogen production by stepwise electrolysis of water based on acidic electrolyte |
| CN114892182A (en) * | 2022-05-10 | 2022-08-12 | 上海嘉氢源科技有限公司 | Three-electrode system-based electrolytic cell for two-step water electrolysis hydrogen production and application thereof |
| CN115029717A (en) * | 2022-07-18 | 2022-09-09 | 中国华能集团清洁能源技术研究院有限公司 | Membrane-free water electrolysis hydrogen production device based on rotary bipolar electrode |
| CN115490374A (en) * | 2022-09-03 | 2022-12-20 | 中国海洋大学 | Method for treating metal processing wastewater by virtue of electrocoagulation coupling PDS oxidation |
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| JP6856293B1 (en) * | 2019-11-15 | 2021-04-07 | 株式会社堤水素研究所 | Reversible fuel cell |
| CN113151843A (en) * | 2021-04-27 | 2021-07-23 | 上海羿沣氢能科技有限公司 | Method and device for producing hydrogen by electrolyzing water step by step |
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| CN101622200A (en) * | 2007-03-20 | 2010-01-06 | 德诺拉工业有限公司 | Electrochemical cell and method for operating the same |
| 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 |
| JP6856293B1 (en) * | 2019-11-15 | 2021-04-07 | 株式会社堤水素研究所 | Reversible fuel cell |
| CN113151843A (en) * | 2021-04-27 | 2021-07-23 | 上海羿沣氢能科技有限公司 | Method and device for producing hydrogen by electrolyzing water step by step |
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