CN108335911B - Microelectronic device for producing hydrogen by decomposing water through sunlight and preparation method thereof - Google Patents
Microelectronic device for producing hydrogen by decomposing water through sunlight and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- 238000004377 microelectronic Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 50
- 239000010408 film Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
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- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
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- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000005611 electricity Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 230000002441 reversible effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/003—Apparatus or processes for encapsulating capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a microelectronic device for producing hydrogen by decomposing water through sunlight and a preparation method thereof, which comprises a CZTS solar cell、BiVO4A photo-anode, a lead and a Pt sheet, wherein the CZTS solar cell, the BiVO4The photoanode and the Pt sheet are connected through the lead, so that the series-structure semiconductor device without external bias is used for preparing hydrogen by photolyzing water, additional power supply is not needed, and the hydrogen can be prepared by spontaneously decomposing water by directly utilizing sunlight, so that all sources of hydrogen energy are sunlight, the sunlight directly generates electricity stably, is nontoxic, has cheap raw materials, can prepare clean, cheap, environment-friendly and reproducible hydrogen energy in the true sense.
Description
Technical Field
The invention relates to the field of solar water decomposition, in particular to a microelectronic device for producing hydrogen by decomposing water through sunlight and a preparation method thereof.
Background
With the progress and development of human society, the demand of human for energy is also increasingly urgent. Meanwhile, combustion products generated in the combustion process of non-renewable energy sources such as coal, petroleum and the like can generate irreversible pollution to the environment. Therefore, it is very important to develop clean energy. Hydrogen energy is considered as one of the most ideal energy sources in the new century by virtue of high energy content, environmental protection and the like as a novel, environment-friendly and renewable clean energy source. The existing photohydrolysis device is unstable, high in cost and easy to pollute the environment. In the prior art, most of the developed devices for decomposing water by sunlight need an external power supply to provide an external bias voltage to excite a semiconductor electrode to crack water to produce hydrogen. The device for generating hydrogen by water photolysis without external electric energy in the true sense can not be realized. Meanwhile, the defects that the utilization rate of visible light is low, the photoelectric conversion efficiency is low and the like exist in some materials, most of the materials can only absorb ultraviolet light, and the ultraviolet light only accounts for 3% of sunlight. For example, in TiO2Photolytic water splitting device as anode material due to TiO2The band gap is wide, only the ultraviolet part in sunlight can be absorbed, and the visible light accounts for 43 percent of the energy of the solar spectrum, so that the photolysis water device has poor response to the sunlight, and the hydrogen production efficiency is naturally not high. Further, although there is a report of hydrogen production by solar water splitting using a photolytic device made of a dye-sensitized semiconductor internationally, the dye-sensitized material is an organic synthetic material, and is liable to exhibit instability upon water splitting and to be corroded by light.
Disclosure of Invention
The invention aims to realize that a series-structure semiconductor device without external bias is used for preparing hydrogen by photolysis of water, and can realize hydrogen preparation by spontaneous decomposition of water by directly utilizing sunlight without an additional power supply, so that all sources of hydrogen energy are sunlight, the sunlight can directly generate electricity stably and is non-toxic, the raw materials are cheap, and the hydrogen energy can be prepared in a clean, cheap, environment-friendly and reproducible manner in the true sense.
BiVO4As a photoanode absorption material, the theoretical band gap is about 2.4ev, and most of sunlight can be absorbed (the theoretical maximum hydrogen production efficiency of the photoanode absorption material is 9.2%). At the same time, BiVO4The conduction band edge of the hydrogen electrode is positioned near the reversible hydrogen electrode, and when the hydrogen electrode obtains lower bias voltage, hydrogen can be produced by cracking water. The CZTS compound semiconductor thin film solar cell has a commercial application potential as a novel solar cell with low cost and environmental friendliness. The absorption layer in the CZTS thin film solar cell structure is CZTS (copper zinc tin sulfide, Cu)2ZnSnS4) The film has the advantages of high light absorption coefficient, rich element reserves, no toxicity and the like. BiVO4Water can be oxidized when a bias of 0.3V relative to the reversible hydrogen electrode is applied, which makes it very attractive for tandem-structure photolytic device applications, BiVO4The photo-anode is combined with the CZTS photo-cathode, and a photo-water splitting self-hydrogen generating device without external bias can be prepared.
Therefore, the invention adopts the following technical scheme:
according to one aspect of the invention, a solar-decomposed aquatic hydrogen microelectronic device is provided, which comprises a CZTS solar cell and a BiVO4A photo-anode, a lead and a Pt sheet, wherein the CZTS solar cell, the BiVO4The photo-anode and the Pt sheet are connected through the lead and packaged into a whole.
According to the inventionIn another aspect of the invention, a solar-decomposed hydrogen production microelectronic device is provided, which comprises a CZTS solar cell and BiVO4A photo-anode, a lead and a Pt sheet, wherein the CZTS solar cell, the BiVO4The light anode and the Pt sheet are connected through the lead, and the CZTS solar cell is connected with the BiVO4The photo anode is packaged into a whole.
According to another aspect of the invention, a solar-decomposed aquatic hydrogen microelectronic device is provided, which comprises a CZTS solar cell and a BiVO4A photo-anode, a lead and a Pt sheet, wherein the CZTS solar cell, the BiVO4The photo-anode and the Pt sheet are connected through a lead to form a series structure.
Further, an optical beam splitter device is also included.
Further, the BiVO4The photo-anode is nano BiVO4A film.
According to another aspect of the invention, a method for preparing a solar energy decomposition water hydrogen production microelectronic device is provided, which comprises the following steps:
the preparation of the CZTS solar cell comprises the following steps,
preparing a CZTS absorbing layer by adopting an electrodeposition method and a vulcanization annealing method in sequence;
preparing a CdS buffer layer on the CZTS absorption layer by a chemical water bath deposition method to serve as an n-type conducting layer;
BiVO4the preparation of the photo-anode comprises the following steps,
preparation of BiVO by electrodeposition4A precursor BiOI of the thin film, and then converting the BiOI precursor into BiVO4Washing off the BiVO by a thin film4V of film surface2O5Cleaning and drying to obtain BiVO4A photo-anode;
the CZTS solar cell and the BiVO4The photoanode and the Pt sheet are connected to form the solar energy decomposition water hydrogen production microelectronic device with a series structure.
Furthermore, the whole series structure is packaged into a whole.
Further, the CZTS solar cell and the BiV are characterized in thatO4The photo anode is packaged into a whole.
Further, in the CZTS battery and the BiVO4An optical beam splitter device is added between the photo-anodes.
Further, the BiVO4The photo-anode is nano BiVO4A film.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
Fig. 1 is a schematic structural diagram of a solar water splitting hydrogen production microelectronic device according to an embodiment.
Fig. 2 is a schematic structural diagram of a solar water splitting hydrogen production microelectronic device according to another embodiment.
Fig. 3 is a schematic structural diagram of a solar water splitting hydrogen production microelectronic device according to another embodiment.
Fig. 4 is a schematic structural diagram of a solar water splitting hydrogen production microelectronic device according to another embodiment.
Detailed Description
Hereinafter, the present invention will be described in further detail with reference to the accompanying drawings.
The preparation of the CZTS solar cell comprises the following steps,
the preparation method of the CZTS absorption layer in the CZTS solar cell comprises the following steps:
the CZTS film is prepared by electrodeposition followed by a sulfidation anneal. The electro-deposition uses an electrochemical workstation, and the electrode system used is a three-electrode device which is a Ag/AgCl reference electrode, a Pt counter electrode and a working electrode of a molybdenum-plated glass substrate respectively. The preparation method specifically comprises the following preparation steps:
firstly, the deposition of a copper layer is carried out, the deposition potential of the copper layer is-0.3V to-0.5V (relative to an Ag/AgCl reference electrode), and the electroplating solution is composed of 0.03mol/L to 0.06mol/L CuSO4·5H2O, 0.01-0.03 mol/L citric acid and 0.03-0.06 mol/L sodium citrate.
Then, a tin layer is deposited, the deposition potential of the tin layer is-0.3V to-0.6V (relative to an Ag/AgCl reference electrode), and the electroplating solution is prepared from 0.03mol/L to 0.06mol/L tin (II) methanesulfonate, 0.5mol/L to 1.5mol/L methanesulfonic acid and 0.5mol/L to 1.5mol/L Empigen BB detergent (dodecyl-tetradecyldimethyl betaine).
Finally, preparing a zinc layer, wherein the deposition potential of the zinc layer is-1.0V to-1.5V (relative to an Ag/AgCl reference electrode), and the electroplating solution is prepared from 0.05mol/L to 1.00mol/L ZnSO4·7H2O, 0.3mol/L to 0.6mol/L of K2SO4Prepared, and the pH value of the electroplating solution is adjusted to 2-4 by using buffer solution.
The sample after electrodeposition is put into a vacuum glass tube and continuously heated for 150 to 250 minutes at the temperature of between 200 and 400 ℃, and then vulcanized for 9 to 11 minutes in a vacuum glass tube filled with sulfur powder containing 5 to 10mg of sulfur element and kept at the temperature of between 500 and 700 ℃. The resulting CZTS film was immersed in a 10% KCN solution for 1 minute to 3 minutes to remove surface contaminants.
The preparation method of the CdS buffer layer in the CZTS solar cell comprises the following steps:
a CdS buffer layer is required to be deposited on the CZTS absorption layer to be used as an n-type conducting layer, and the CdS buffer layer is prepared by a chemical water bath deposition method, and the method comprises the following specific steps: immersing the CZTS film prepared in the solution at a concentration of 10 mmol/L-12 mmol/LCdSO4，0.20mol/L～0.30mol/L SC(NH2)2And 10mol/L to 12mol/L of NH4The solution prepared by OH reacts for 6 to 9 minutes in water bath at 50 to 70 ℃. Finally, a CdS buffer layer can be deposited on the CZTS film.
BiVO4BiVO in photo-anode4The preparation method of the film comprises the following steps:
firstly, preparing BiVO by an electrodeposition method4The precursor BiOI of the film and the electro-deposition device still consist of a three-electrode system, namely an Ag/AgCl reference electrode, a Pt counter electrode and a working electrode. The method comprises the following specific steps:
containing 0.0070-0.0080 mol/L of Bi (NO)3)30.3mol/L to 0.5mol/L NaI and 100ml of HNO with pH value of 1 to 23The solution was mixed with 45ml of 0.2mol/L to 0.4mol/L benzoquinone solution prepared with ethanol to form an electroplating solution. Stirring for 20-40 min after mixing,after stirring, standing for a period of time to obtain static potential, and then beginning electrodeposition.
The reference electrode was placed approximately 1em to 3cm behind the right of the glass side of the working electrode. The initial deposition potential of 3s to 6s was-0.2V to-0.4V (relative to an Ag/AgCl reference electrode), and the purpose of setting the initial deposition potential was to prevent the BiOI from peeling off the ITO substrate.
Immediately after the initial electrodeposition, the electrode potential is adjusted to-0.05V-0.15V (relative to an Ag/AgCl reference electrode), the electrodeposition is carried out for 5-7 minutes, finally, a BiOI film with the thickness of about 500nm is deposited on an ITO substrate, and a sample is cleaned and dried.
Then the BiOI precursor is converted into BiVO4The BiOI precursor prepared is firstly soaked in 0.3-0.5 mol/L vanadyl acetylacetonate (DMSO) solution for 15-25 s. Excess vanadium source solution was removed by rapid contact between the bottom edge of the electrode and the filter paper.
The electrode is then transferred to a muffle furnace and is first heated to 100-130 ℃ before annealing. The annealing temperature is first raised to 200-350 c at a rate of 1 c per minute, then to 350-500 c at a rate of 2 c per minute, and this temperature is maintained for 0.5-1.5 hours. The initial slow temperature ramp is BiVO4The key point is that the thin film grows uniformly and tightly on the whole electrode.
After the annealing is finished, the whole electrode is soaked in NaOH solution of 0.03-0.06 mol/L for 3-6 minutes and slightly stirred to wash off BiVO4V of film surface2O5. Finally, cleaning and drying to obtain BiVO4And a photo-anode.
The CZTS solar cell and BiVO are combined4The photo-anode is connected to form a serial structure of photo-water splitting devices.
In one embodiment, BiVO is formed by conducting wires4The ITO layer of the photo-anode is connected with the molybdenum-plated layer of the CZTS solar cell, a lead is led out from the ITO layer on the surface of the CZTS solar cell and connected with a Pt sheet, and hydrogen is separated out from the surface of the Pt sheet when the Pt sheet is used as a photo-cathode to decompose water. The Pt sheet was fixed to the back of the CZTS cell with glue and the whole structure was encapsulatedIs integrated into a whole. When water is photolyzed, the whole device is immersed in the electrolyte to absorb the sunlight to decompose the water. The device has the advantages that the device is portable and simple, and the whole device is only required to be immersed in electrolyte and irradiated by sunlight when water is decomposed.
In another embodiment, BiVO is wired4The ITO layer of the photo-anode is connected with the molybdenum-plated layer of the CZTS solar cell, a lead is led out from the ITO layer on the surface of the CZTS solar cell and connected with a Pt sheet, and hydrogen is separated out from the surface of the Pt sheet when the Pt sheet is used as a photo-cathode to decompose water. The difference from the above embodiment is that the device shown is a CZTS cell and BiVO4The photo-anodes are connected together, the whole device is still immersed in the electrolyte when water is decomposed, the Pt sheet electrode is not fixed on the back of the CZTS battery by glue and can move freely in the electrolyte, the Pt sheet ring is not packaged, and the contact area of the Pt electrode and the electrolyte is increased, so that hydrogen gas is beneficially separated out.
In another embodiment, BiVO is wired4The ITO layer of the photo-anode is connected with the molybdenum-plated layer of the CZTS solar cell, a lead is led out from the ITO layer on the surface of the CZTS solar cell and connected with a Pt sheet, and the Pt sheet is connected with BiVO4The photoanode is placed in the electrolyte together and the CZTS cell is exposed to air to fully absorb sunlight. When water is cracked, hydrogen is separated out on the surface of the Pt sheet electrode, and oxygen is separated out on the BiVO4And (4) separating out the surface of the photo-anode. The device is formed by combining a CZTS battery and BiVO4The photo anode is connected by a lead but is not packaged into a whole. BiVO in water decomposition4The light anode is immersed in the electrolyte to receive sunlight irradiation, and the CZTS solar cell is exposed in the air to receive sunlight irradiation.
In another embodiment, BiVO is wired4The ITO layer of the photo-anode is connected with the molybdenum-plated layer of the CZTS solar cell, a lead is led out from the ITO layer on the surface of the CZTS solar cell and connected with a Pt sheet, and the Pt sheet is connected with BiVO4The photoanode is put into the electrolyte together and is arranged in a CZTS battery and a BiVO4An optical beam splitter device is added between the photo-anodes. The light splitter enables sunlight with the wavelength larger than 515nm to be absorbed by the CZTS batterySolar quilt BiVO with wavelength less than 515nm4The light anode absorbs the light, so that the utilization rate of the whole device to sunlight is greatly improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A microelectronic device for producing hydrogen by decomposing water with sunlight is characterized by comprising a CZTS solar cell and a BiVO4A photo-anode, a lead and a Pt sheet; the CZTS solar cell comprises a first substrate, a first electrode layer, a CZTS layer, an n-type conducting layer and a second electrode layer, wherein the first substrate, the first electrode layer, the CZTS layer, the n-type conducting layer and the second electrode layer are sequentially stacked; the BiVO4The photo-anode comprises a second substrate, an ITO layer and a BiVO which are sequentially stacked4A film; the second electrode layer of the CZTS solar cell is laminated on one side, opposite to the ITO layer, of the second substrate, and the Pt layer is laminated on the side, opposite to the first electrode layer, of the first substrate; wherein the second electrode layer of the CZTS solar cell is connected with the Pt sheet through a lead, and the BiVO4And the ITO layer of the photo-anode is connected with the first electrode layer of the CZTS solar cell through a lead and packaged into a whole.
2. A microelectronic device for producing hydrogen by decomposing water with sunlight is characterized by comprising a CZTS solar cell and a BiVO4A photo-anode, a lead and a Pt sheet; the CZTS solar cell comprises a first substrate, a first electrode layer, a CZTS layer, an n-type conducting layer and a second electrode layer, wherein the first substrate, the first electrode layer, the CZTS layer, the n-type conducting layer and the second electrode layer are sequentially stacked; the BiVO4The photo-anode comprises a second substrate, an ITO layer and a BiVO which are sequentially stacked4A film; the second electrode of the CZTS solar cellThe side, opposite to the ITO layer, of the second substrate is laminated; wherein the second electrode layer of the CZTS solar cell is connected with the Pt sheet through a lead, and the BiVO4The ITO layer of the photo-anode is connected with the first electrode layer of the CZTS solar cell through a lead, and the CZTS solar cell is connected with the BiVO4The photo anode is packaged into a whole.
3. A microelectronic device for producing hydrogen by decomposing water with sunlight is characterized by comprising a CZTS solar cell and a BiVO4The CZTS solar cell comprises a first substrate, a first electrode layer, a CZTS layer, an n-type conducting layer and a second electrode layer, wherein the first substrate, the first electrode layer, the CZTS layer, the n-type conducting layer and the second electrode layer are sequentially stacked; the BiVO4The photo-anode comprises a second substrate, an ITO layer and a BiVO which are sequentially stacked4A film;
wherein the second electrode layer of the CZTS solar cell is connected with the Pt sheet through a lead, and the BiVO4The ITO layer of the photo-anode is connected with the first electrode layer of the CZTS solar cell through a lead; when decomposing water, only the BiVO is added4The photo-anode and the Pt sheet are placed in the electrolyte.
4. A device according to claim 3, further comprising optical beam splitter means.
5. The device of any of claims 1-3, wherein the BiVO is4The film is nanometer BiVO4A film.
6. A method of manufacturing a solar-decomposed aquatic hydrogen microelectronic device according to one of claims 1 to 5, characterized by comprising the steps of:
the preparation of the CZTS solar cell comprises the following steps,
preparing a CZTS absorbing layer by adopting an electrodeposition method and a vulcanization annealing method in sequence;
preparing a CdS buffer layer on the CZTS absorption layer by a chemical water bath deposition method to serve as an n-type conducting layer;
BiVO4the preparation of the photo-anode comprises the following steps,
preparation of BiVO by electrodeposition4A precursor BiOI of the thin film, and then converting the precursor BiOI into BiVO4Washing off the BiVO by a thin film4V of film surface2O5Cleaning and drying to obtain the BiVO4A photo-anode;
the CZTS solar cell and the BiVO4The photoanode and the Pt sheet are connected to form the solar energy decomposition water hydrogen production microelectronic device with a series structure.
7. The method of claim 6, wherein the series structure is entirely encapsulated as a single piece.
8. The method of claim 6, wherein the CZTS solar cell is placed in contact with the BiVO4The photo anode is packaged into a whole.
9. The method of claim 6, wherein the CZTS solar cell and the BiVO are fabricated using a single process4An optical beam splitter device is added between the photo-anodes.
10. The method according to claim 6, wherein the BiVO is washed off4V of film surface2O5Previously, the precursor BiOI was converted into BiVO4The film also includes transferring the photoanode to a muffle furnace to first preheat to 100-130 deg.C and then anneal, the annealing temperature is first increased to 200-350 deg.C at a rate of 1 deg.C per minute, then increased to 350-500 deg.C at a rate of 2 deg.C per minute, and maintained at this temperature for 0.5-1.5 hours.
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