CN114351176B - Method and device for producing hydrogen by water decomposition - Google Patents
Method and device for producing hydrogen by water decomposition Download PDFInfo
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Abstract
A method for producing hydrogen by water splitting and a device thereof, wherein the method comprises the following steps: a niobium doped titanium dioxide transparent conductive layer is arranged on one side of the N-type semiconductor silicon and one side of the P-type semiconductor silicon respectively, and a conductive metal layer is arranged on the other side of the N-type semiconductor silicon to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode; the N-type silicon photoelectrode and the P-type silicon photoelectrode are respectively used as an anode and a cathode to be connected into an electrolyzer; the thermoelectric semiconductor is driven by the temperature difference to generate electric energy to drive the N-type silicon photoelectrode and the P-type silicon photoelectrode to carry out water decomposition to prepare hydrogen. The method utilizes the photo-thermal conversion of the sun to drive the thermoelectric semiconductor to provide bias voltage to promote the silicon photoelectrode to realize water decomposition, and avoids the reduction of water decomposition efficiency caused by the limitation relation between photovoltaic cell photovoltage and photocurrent. Meanwhile, the corrosion-resistant niobium doped titanium dioxide transparent conductive layer is utilized to realize the high-efficiency light absorption and high-efficiency carrier migration of the silicon photoelectrode, so that the efficiency and stability of the water decomposition of the silicon photoelectrode are improved.
Description
Technical Field
The invention relates to the field of water decomposition, in particular to a method and a device for producing hydrogen by utilizing solar energy and a silicon photoelectrode to carry out water decomposition.
Background
In recent decades, research for finding new energy has been receiving more and more attention as global energy demand continues to increase. The hydrogen energy is used as a secondary energy source, has the advantages of cleanness, high efficiency, storability, transportation and the like, is widely regarded as an ideal pollution-free green energy source in the new century, and is therefore highly valued by various countries.
The hydrogen production by photolysis of water is a mode of hydrogen production, and the principle is as follows: light is radiated on a semiconductor, electrons in the semiconductor are stimulated to transition from a valence band to a conduction band when the radiated energy is larger than or equal to the forbidden band width of the semiconductor, holes are reserved in the valence band, the electrons and the holes are separated, and then water is reduced to hydrogen or oxidized to oxygen at different positions of the semiconductor respectively.
It is found that the external voltage of the photodecomposition water must be greater than 1.6V to realize the full reaction of the water decomposition based on the thermodynamic and kinetic conditions of the water decomposition. At present, the voltage generated by a semiconductor photoelectrode (such as a silicon photoelectrode) under the irradiation of simulated sunlight is often insufficient to realize the water decomposition reaction. Therefore, a bias voltage needs to be applied to the silicon photoelectrode, and the silicon photoelectrode can be driven by a silicon photovoltaic cell to carry out water decomposition, but due to the limiting relationship between the photovoltage and the photocurrent of the silicon photovoltaic cell, the photocurrent density of the silicon photoelectrode is reduced, so that the conversion efficiency of preparing hydrogen by means of solar energy is reduced. In addition, a thicker corrosion-resistant protective layer is required for the silicon photoelectrode to exhibit stable photoelectric performance, and a protective layer which is too thick is often unfavorable for absorption of incident light or transmission of photogenerated carriers by the silicon photoelectrode, thereby causing degradation of photoelectric performance.
Therefore, in order to address the above drawbacks and meet the energy-saving and environment-friendly requirements, effective innovation of the existing technology is needed.
Disclosure of Invention
The invention aims to provide a method and a device for producing hydrogen by water decomposition, wherein a thermoelectric semiconductor is driven by photo-thermal conversion of the sun to provide bias voltage to promote a silicon photoelectrode to realize water decomposition, so that the reduction of water decomposition efficiency caused by the limiting relationship between photovoltaic cell photovoltage and photocurrent is avoided. Meanwhile, the corrosion-resistant niobium doped titanium dioxide transparent conductive layer is utilized to realize the high-efficiency light absorption and high-efficiency carrier migration of the silicon photoelectrode, so that the efficiency and stability of the water decomposition of the silicon photoelectrode are improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for producing hydrogen by water splitting, comprising the steps of:
s1, arranging a niobium doped titanium dioxide transparent conductive layer on one side of N-type and P-type semiconductor silicon respectively, and arranging a conductive metal layer on the other side to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
s2, the N-type silicon photoelectrode and the P-type silicon photoelectrode are respectively used as an anode and a cathode to be connected into an electrolyzer;
s3, driving the N-type silicon photoelectrode and the P-type silicon photoelectrode to carry out water splitting hydrogen production by using the thermoelectric device;
further, in step S1, a transparent conductive layer of niobium doped titanium dioxide is deposited on one side of the N-type and P-type semiconductor silicon by using a magnetron sputtering, laser pulse or surface spraying method, and the transparent conductive layer of niobium doped titanium dioxide is subjected to heat treatment, and after the heat treatment is completed, a conductive metal layer is deposited on the other side of the N-type and P-type semiconductor silicon by using a magnetron sputtering, laser pulse or surface spraying method, so as to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
further, in step S2, a catalyst for producing hydrogen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer of the P-type silicon photoelectrode, and a catalyst for producing oxygen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer of the N-type silicon photoelectrode;
further, preparing a catalyst for producing hydrogen and oxygen by water decomposition by adopting a method of magnetron sputtering, pulse laser or electron beam evaporation;
further, in step S3, one end of the P-type thermoelectric semiconductor and one end of the N-type thermoelectric semiconductor are thermally connected to the same heat source, and the other ends of the P-type thermoelectric semiconductor and the N-type thermoelectric semiconductor are respectively thermally connected to a heat dissipation medium, so as to form a thermoelectric device; it should be noted that, the other ends of the P-type thermoelectric semiconductor and the N-type thermoelectric semiconductor are respectively connected with a heat dissipation medium in a heat conduction manner, which means that the P-type thermoelectric semiconductor and the N-type thermoelectric semiconductor are not connected to the same heat dissipation medium, and the following is the same;
further, in step S3, the P-type thermoelectric semiconductor is electrically connected to the conductive metal layer of the N-type silicon photoelectrode, and the N-type thermoelectric semiconductor is electrically connected to the conductive metal layer of the P-type silicon photoelectrode, so as to drive the silicon photoelectrode by the thermoelectric device; the current flows from the P-type thermoelectric semiconductor to the N-type silicon photoelectrode, and then flows from the P-type silicon photoelectrode to the N-type thermoelectric semiconductor to form an electrolytic loop;
further, the heat source is prepared by dispersing at least one of a nano carbon material, MXene, cuprous sulfide or cuprous telluride in a transparent high-boiling-point solvent, the heat source is used for photo-thermal conversion storage, the nano carbon material comprises graphite, carbon nano tubes, graphene, carbon nano particles and carbon quantum dots, the MXene is carbide, nitride or carbonitride of two-dimensional transition metal, and the high-boiling-point solvent comprises ethylene glycol, glycerol and silicone oil;
further, the P-type thermoelectric semiconductor is a P-type bismuth telluride thermoelectric semiconductor, and the N-type thermoelectric semiconductor is an N-type bismuth telluride thermoelectric semiconductor.
The invention also provides a device for producing hydrogen by water splitting, which comprises a silicon photoelectrode electrolyzer and a thermoelectric device, wherein the silicon photoelectrode electrolyzer comprises an N-type silicon photoelectrode and a P-type silicon photoelectrode which are respectively used as an anode and a cathode, the N-type silicon photoelectrode comprises N-type semiconductor silicon, a niobium-doped titanium dioxide transparent conductive layer arranged on one side of the N-type semiconductor silicon and a conductive metal layer arranged on the other side of the N-type semiconductor silicon, the P-type silicon photoelectrode comprises P-type semiconductor silicon, a niobium-doped titanium dioxide transparent conductive layer arranged on one side of the P-type semiconductor silicon and a conductive metal layer arranged on the other side of the P-type semiconductor silicon, and the thermoelectric device is respectively connected with the N-type silicon photoelectrode and the P-type silicon photoelectrode;
further, the thicknesses and niobium contents of the niobium-doped titanium dioxide transparent conductive layers on the N-type silicon photoelectrode and the P-type silicon photoelectrode are the same or different, and the light transmittance, the conductivity and the work function of the niobium-doped titanium dioxide layer are adjusted through the thicknesses and the niobium contents;
further, a catalyst for producing hydrogen by water decomposition is deposited on the surface of the niobium-doped titanium dioxide transparent conductive layer of the P-type silicon photoelectrode, and a catalyst for producing oxygen by water decomposition is deposited on the surface of the niobium-doped titanium dioxide transparent conductive layer of the N-type silicon photoelectrode;
further, the thermoelectric device comprises a P-type thermoelectric semiconductor, an N-type thermoelectric semiconductor, a heat source and a heat dissipation medium, wherein one ends of the P-type thermoelectric semiconductor and the N-type thermoelectric semiconductor are connected to the same heat source in a heat conduction manner, the other ends of the P-type thermoelectric semiconductor and the N-type thermoelectric semiconductor are respectively connected with the heat dissipation medium in a heat conduction manner, the conductive metal layers of the P-type thermoelectric semiconductor and the N-type silicon photoelectrode are electrically connected, and the conductive metal layers of the N-type thermoelectric semiconductor and the P-type silicon photoelectrode are electrically connected;
further, the heat source member includes a high boiling point solvent in which at least one of a nanocarbon material, MXene, cuprous sulfide, or cuprous telluride is dispersed;
further, the nano carbon material comprises graphite, carbon nano tubes, graphene, carbon nano particles and carbon quantum dots;
further, the MXene includes a carbide, nitride, or carbonitride of a two-dimensional transition metal;
further, the high boiling point solvent includes ethylene glycol, glycerol, and silicone oil;
further, the P-type thermoelectric semiconductor is a P-type bismuth telluride thermoelectric semiconductor, and the N-type thermoelectric semiconductor is an N-type bismuth telluride thermoelectric semiconductor.
The beneficial effects of the invention are as follows:
1) The niobium-doped titanium dioxide transparent conductive layer is arranged on the silicon photoelectric electrode, and the stability and light absorption of the silicon photoelectric electrode in electrolyte are improved by utilizing the niobium-doped titanium dioxide transparent conductive layer, so that the high-efficiency and stable water decomposition performance of the silicon photoelectric electrode is realized;
2) The light transmittance and the conductivity of the niobium-doped titanium dioxide layer are optimized through heat treatment, so that the light absorption property and the photogenerated carrier migration capability of the silicon photoelectrode in electrolyte are further improved;
3) The thermoelectric semiconductor utilizes the heat source to generate electric energy to drive the silicon photoelectrode to decompose water to prepare hydrogen and oxygen, and utilizes clean renewable solar energy to drive, so that the problem that the bias voltage generated by the single silicon photoelectrode is insufficient to decompose water is solved, the use of a non-renewable or pollution driving source can be avoided, the loss of non-renewable energy sources is reduced, and the environmental protection performance is improved.
Drawings
FIG. 1 is a schematic view of an apparatus for producing hydrogen by water splitting according to an embodiment of the present invention;
in the figure:
11. n-type semiconductor silicon; 12. p-type semiconductor silicon; 13. a niobium doped titanium dioxide transparent conductive layer; 14. a conductive metal layer; 15. an oxygen-generating catalyst; 16. a hydrogen-producing catalyst;
21. a P-type bismuth telluride thermoelectric semiconductor; 22. an N-type bismuth telluride thermoelectric semiconductor; 23. a heat source; 24. a water tank;
3. an electric wire; 4. an aqueous electrolyte.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. It should be noted that the drawings are in a very simplified form and are all to a non-precise scale, merely for convenience and clarity in aiding in the description of embodiments of the invention.
As shown in fig. 1, in one embodiment of the apparatus for producing hydrogen by water splitting according to the present invention, a silicon photoelectrode electrolyzer and a thermoelectric device are included;
the silicon photoelectrode electrolyzer comprises an N-type silicon photoelectrode and a P-type silicon photoelectrode, the N-type silicon photoelectrode and the P-type silicon photoelectrode are inserted into the aqueous electrolyte 4 to respectively serve as an anode and a cathode in the electrolyzer, the N-type silicon photoelectrode comprises an N-type semiconductor silicon 11, a niobium-doped titanium dioxide transparent conductive layer 13 arranged on one side of the N-type semiconductor silicon 11 and a conductive metal layer 14 arranged on the other side of the N-type semiconductor silicon 11, and the P-type silicon photoelectrode comprises a P-type semiconductor silicon 12, a niobium-doped titanium dioxide transparent conductive layer 13 arranged on one side of the P-type semiconductor silicon 12 and a conductive metal layer 14 arranged on the other side of the P-type semiconductor silicon 12. In addition, in order to improve the electrolysis efficiency of the silicon photoelectrode electrolyzer, a catalyst 16 for producing hydrogen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode by adopting a method of magnetron sputtering, pulse laser or electron beam evaporation, and a catalyst 15 for producing oxygen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode by adopting a method of magnetron sputtering, pulse laser or electron beam evaporation;
the thermoelectric device includes a P-type thermoelectric semiconductor made of a P-type thermoelectric material, an N-type thermoelectric semiconductor made of an N-type thermoelectric material, a heat source 23, and a heat dissipation medium. In this embodiment, the P-type thermoelectric semiconductor is a P-type bismuth telluride thermoelectric semiconductor 21, the N-type thermoelectric semiconductor is an N-type bismuth telluride thermoelectric semiconductor 22, the heat source 23 is silicone oil with graphite and cuprous telluride dispersed therein, and the heat dissipation medium is a water tank 24. The silicon oil dispersed with graphite and cuprous telluride is placed in a transparent container and placed under sunlight, the upper end of the P-type bismuth telluride thermoelectric semiconductor 21 is fixed by a heat conducting adhesive and the bottom of the container in which the heat source 23 is placed, the lower end of the P-type bismuth telluride thermoelectric semiconductor is fixed by the heat conducting adhesive and the top of the water tank 24, the upper end of the N-type bismuth telluride thermoelectric semiconductor 22 is fixed by the heat conducting adhesive and the bottom of the same heat source 23, the lower end of the N-type bismuth telluride thermoelectric semiconductor is fixed by the heat conducting adhesive and the top of the other water tank 24, the bottom of the P-type bismuth telluride thermoelectric semiconductor is electrically connected by the electric wire 3 and the conductive metal layer 14 on the N-type silicon photoelectric electrode, and the bottom of the N-type bismuth telluride thermoelectric semiconductor is electrically connected by the electric wire 3 and the conductive metal layer 14 on the P-type silicon photoelectric electrode. Thus, the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22 are used to generate electric energy, so as to drive the silicon photoelectrode to undergo a full water decomposition reaction.
The hydrogen production device by adopting the water splitting method can adopt the following hydrogen production method.
Example 1
1) A transparent conductive layer 13 of niobium doped titanium dioxide with the same thickness but different niobium content is deposited on one side of the N-type semiconductor silicon 11 and the P-type semiconductor silicon 12 respectively by using a magnetron sputtering method, for example, a transparent conductive layer 13 of niobium doped titanium dioxide with the thickness of 400nm and the niobium content of 2at.% is deposited on one side of the N-type semiconductor silicon 11, and a transparent conductive layer 13 of niobium doped titanium dioxide with the thickness of 400nm and the niobium content of 5at.% is deposited on one side of the P-type semiconductor silicon 12;
2) The niobium-doped titanium dioxide transparent conductive layer 13 was subjected to Ar/H at a flow rate of 30sccm 2 Heat-treating (95:5, v/v) in a mixed reducing atmosphere at 450 ℃ for 30min;
3) Depositing a conductive metal layer 14 on the other side of the N-type semiconductor silicon 12 and the other side of the P-type semiconductor silicon 12 respectively by utilizing a magnetron sputtering method to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
4) The catalyst 15 for producing oxygen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode by adopting magnetron sputtering or pulse laser, and the catalyst 16 for producing hydrogen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode by adopting magnetron sputtering or pulse laser. For example, a transition metal or a transition metal oxide such as Ni, niO or CoO is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode x Preparing transition metal alloy, such as Pt or NiMo alloy, on the surface of the niobium doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode;
5) The silicon oil dispersed with graphite and cuprous telluride is arranged in a transparent container and placed in sunlight, the upper ends of the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22 are fixed on the bottom of a container of a heat source 23 through a heat conducting adhesive, and the lower ends of the P-type bismuth telluride thermoelectric semiconductor and the N-type bismuth telluride thermoelectric semiconductor are respectively fixed on two water tanks 24 through the heat conducting adhesive;
6) The conductive metal layer 14 of the P-type thermoelectric bismuth telluride semiconductor 21 and the conductive metal layer 14 of the N-type silicon photoelectrode are connected through the electric wire 3, the N-type bismuth telluride thermoelectric semiconductor 22 and the conductive metal layer 14 of the P-type silicon photoelectrode are connected through the electric wire 3, electric energy driving of the N-type silicon photoelectrode and the P-type silicon photoelectrode is achieved through the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22, and the N-type silicon photoelectrode and the P-type silicon photoelectrode are driven to electrolyze water to respectively prepare hydrogen and oxygen.
Example 2
1) A transparent conductive layer 13 of niobium-doped titanium dioxide having different thickness and niobium content is deposited on one side of the N-type semiconductor silicon 11 and the P-type semiconductor silicon 12 respectively by a laser pulse method, for example, a transparent conductive layer 13 of niobium-doped titanium dioxide having a thickness of 500nm and a niobium content of 1at.% is deposited on one side of the N-type semiconductor silicon 11, and a transparent conductive layer 13 of niobium-doped titanium dioxide having a thickness of 300nm and a niobium content of 6at.% is deposited on one side of the P-type semiconductor silicon 12;
2) The niobium-doped titanium dioxide transparent conductive layer 13 was subjected to Ar/H at a flow rate of 30sccm 2 Heat-treating (95:5, v/v) in a mixed reducing atmosphere at 450 ℃ for 30min;
3) Depositing a conductive metal layer 14 on the other side of the N-type semiconductor silicon 12 and the other side of the P-type semiconductor silicon 12 respectively by utilizing a magnetron sputtering method to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
4) The catalyst 15 for producing oxygen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode by adopting magnetron sputtering or pulse laser, and the catalyst 16 for producing hydrogen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode by adopting magnetron sputtering or pulse laser. For example, a transition metal or a transition metal oxide such as Ni, niO or CoO is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode x Preparing transition metal alloy, such as Pt or NiMo alloy, on the surface of the niobium doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode;
5) The silicon oil dispersed with graphite and cuprous telluride is arranged in a transparent container and placed in sunlight, the upper ends of the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22 are fixed on the bottom of a container of a heat source 23 through a heat conducting adhesive, and the lower ends of the P-type bismuth telluride thermoelectric semiconductor and the N-type bismuth telluride thermoelectric semiconductor are respectively fixed on two water tanks 24 through the heat conducting adhesive;
6) The conductive metal layer 14 of the P-type bismuth telluride thermoelectric semiconductor 21 and the conductive metal layer 14 of the N-type silicon photoelectrode are connected through the electric wire 3, the N-type bismuth telluride thermoelectric semiconductor 22 and the conductive metal layer 14 of the P-type silicon photoelectrode are connected through the electric wire 3, electric energy driving of the N-type silicon photoelectrode and the P-type silicon photoelectrode is achieved through the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22, and the N-type silicon photoelectrode and the P-type silicon photoelectrode are driven to electrolyze water to respectively prepare hydrogen and oxygen.
Example 3
1) A transparent conductive layer 13 of niobium doped titanium dioxide with different thickness and same niobium content is deposited on one side of the N-type semiconductor silicon 11 and the P-type semiconductor silicon 12 respectively by using a surface spraying method, for example, a transparent conductive layer 13 of niobium doped titanium dioxide with thickness of 600nm and niobium content of 0.5at.% is deposited on one side of the N-type semiconductor silicon 11, and a transparent conductive layer 13 of niobium doped titanium dioxide with thickness of 200nm and niobium content of 0.5at.% is deposited on one side of the P-type semiconductor silicon 12;
2) The niobium-doped titanium dioxide transparent conductive layer 13 was subjected to Ar/H at a flow rate of 30sccm 2 Heat-treating (95:5, v/v) in a mixed reducing atmosphere at 450 ℃ for 30min;
3) Depositing a conductive metal layer 14 on the other side of the N-type semiconductor silicon 12 and the other side of the P-type semiconductor silicon 12 respectively by utilizing a magnetron sputtering method to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
4) The catalyst 15 for producing oxygen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode by adopting magnetron sputtering or pulse laser, and the catalyst 16 for producing hydrogen by water decomposition is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode by adopting magnetron sputtering or pulse laser. For example, a transition metal or a transition metal oxide such as Ni, niO or CoO is prepared on the surface of the niobium-doped titanium dioxide transparent conductive layer 13 of the N-type silicon photoelectrode x Preparing transition metal alloy, such as Pt or NiMo alloy, on the surface of the niobium doped titanium dioxide transparent conductive layer 13 of the P-type silicon photoelectrode;
5) The silicon oil dispersed with graphite and cuprous telluride is arranged in a transparent container and placed in sunlight, the upper ends of the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22 are fixed on the bottom of a container of a heat source 23 through a heat conducting adhesive, and the lower ends of the P-type bismuth telluride thermoelectric semiconductor and the N-type bismuth telluride thermoelectric semiconductor are respectively fixed on two water tanks 24 through the heat conducting adhesive;
6) The conductive metal layer 14 of the P-type bismuth telluride thermoelectric semiconductor 21 and the conductive metal layer 14 of the N-type silicon photoelectrode are connected through the electric wire 3, the N-type bismuth telluride thermoelectric semiconductor 22 and the conductive metal layer 14 of the P-type silicon photoelectrode are connected through the electric wire 3, electric energy driving of the N-type silicon photoelectrode and the P-type silicon photoelectrode is achieved through the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22, and the N-type silicon photoelectrode and the P-type silicon photoelectrode are driven to electrolyze water to respectively prepare hydrogen and oxygen.
The foregoing embodiments can provide the required voltage for the water decomposition total reaction for the N-type silicon photoelectrode and the P-type silicon photoelectrode by means of the P-type bismuth telluride thermoelectric semiconductor 21 and the N-type bismuth telluride thermoelectric semiconductor 22.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. A method for producing hydrogen by water splitting, comprising the steps of:
s1, arranging a niobium doped titanium dioxide transparent conductive layer on one side of N-type and P-type semiconductor silicon respectively, and arranging a conductive metal layer on the other side to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode;
s2, the N-type silicon photoelectrode and the P-type silicon photoelectrode are respectively used as an anode and a cathode to be connected into an electrolyzer;
s3, one end of the P-type thermoelectric semiconductor and one end of the N-type thermoelectric semiconductor are connected to the same heat source in a heat conduction mode, the other ends of the P-type thermoelectric semiconductor and the N-type silicon photoelectrode are connected in a heat conduction mode, the P-type thermoelectric semiconductor and the N-type silicon photoelectrode are connected in an electric conduction mode, the N-type thermoelectric semiconductor is connected with the P-type silicon photoelectrode in an electric conduction mode, and the heat source is prepared by dispersing at least one of a nano carbon material, MXene, cuprous sulfide or cuprous telluride in a transparent high-boiling-point solvent, and the N-type silicon photoelectrode and the P-type silicon photoelectrode are driven by a thermoelectric device to carry out water decomposition hydrogen production.
2. The method for producing hydrogen by water splitting according to claim 1, wherein in the step S1, a niobium-doped titanium dioxide transparent conductive layer is deposited on one side of the N-type and P-type semiconductor silicon by using a magnetron sputtering, laser pulse or surface spraying method, and the niobium-doped titanium dioxide transparent conductive layer is subjected to heat treatment, and a conductive metal layer is deposited on the other side of the N-type and P-type semiconductor silicon by using a magnetron sputtering, laser pulse or surface spraying method, respectively, so as to obtain an N-type silicon photoelectrode and a P-type silicon photoelectrode.
3. The method for producing hydrogen by water splitting according to claim 1, further comprising preparing a catalyst for producing hydrogen by water splitting on the surface of the niobium-doped titanium dioxide transparent conductive layer of the P-type silicon photoelectrode and preparing a catalyst for producing oxygen by water splitting on the surface of the niobium-doped titanium dioxide transparent conductive layer of the N-type silicon photoelectrode in step S2.
4. The method of producing hydrogen from water splitting as defined in claim 1 wherein said P-type thermoelectric semiconductor is a P-type bismuth telluride thermoelectric semiconductor and said N-type thermoelectric semiconductor is an N-type bismuth telluride thermoelectric semiconductor.
5. The device for producing hydrogen by water splitting is characterized by comprising a silicon photoelectrode electrolyzer and a thermoelectric device, wherein the silicon photoelectrode electrolyzer comprises an N-type silicon photoelectrode and a P-type silicon photoelectrode which are respectively used as an anode and a cathode, the N-type silicon photoelectrode comprises N-type semiconductor silicon, a niobium doped titanium dioxide transparent conductive layer arranged on one side of the N-type semiconductor silicon and a conductive metal layer arranged on the other side of the N-type semiconductor silicon, the P-type silicon photoelectrode comprises P-type semiconductor silicon, a niobium doped titanium dioxide transparent conductive layer arranged on one side of the P-type semiconductor silicon and a conductive metal layer arranged on the other side of the P-type semiconductor silicon, the thermoelectric device comprises a P-type thermoelectric semiconductor, an N-type thermoelectric semiconductor, a heat source and a heat dissipation medium, one end of the P-type thermoelectric semiconductor and one end of the N-type semiconductor are in thermal conduction connection with the same heat source, the other end of the P-type thermoelectric semiconductor and the other end of the N-type thermoelectric semiconductor are in thermal conduction with the medium, the P-type semiconductor and the N-type semiconductor are in thermal conduction with the heat source, and the copper sulfide is in thermal conduction with the heat source, and the copper sulfide is in thermal conduction with the heat dissipation medium, and the thermoelectric carbon nano-doped silicon has at least one of the copper sulfide has a high boiling point, and has a copper sulfide conductive material in the thermoelectric carbon conductive layer.
6. The apparatus for producing hydrogen by water splitting as defined in claim 5, wherein said niobium doped titanium dioxide transparent conductive layers on said N-type silicon photoelectrode and said P-type silicon photoelectrode have the same or different thickness and niobium content.
7. The apparatus for producing hydrogen by water splitting as defined in claim 5, wherein a catalyst for producing hydrogen by water splitting is deposited on the surface of said niobium-doped titanium dioxide transparent conductive layer of said P-type silicon photoelectrode, and a catalyst for producing oxygen by water splitting is deposited on the surface of said niobium-doped titanium dioxide transparent conductive layer of said N-type silicon photoelectrode.
8. The apparatus for producing hydrogen from water splitting as defined in claim 5 wherein the P-type thermoelectric semiconductor is a P-type bismuth telluride thermoelectric semiconductor and the N-type thermoelectric semiconductor is an N-type bismuth telluride thermoelectric semiconductor.
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| CN202111453199.XA CN114351176B (en) | 2021-12-01 | 2021-12-01 | Method and device for producing hydrogen by water decomposition |
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| CN202111453199.XA CN114351176B (en) | 2021-12-01 | 2021-12-01 | Method and device for producing hydrogen by water decomposition |
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