CN105862061A - Full-green reaction device for hydrolytic hydrogen production of photo-electrochemical battery - Google Patents
Full-green reaction device for hydrolytic hydrogen production of photo-electrochemical battery Download PDFInfo
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- CN105862061A CN105862061A CN201610210586.3A CN201610210586A CN105862061A CN 105862061 A CN105862061 A CN 105862061A CN 201610210586 A CN201610210586 A CN 201610210586A CN 105862061 A CN105862061 A CN 105862061A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a full-green reaction device for hydrolytic hydrogen production of a photo-electrochemical battery. The device comprises a hydro-generator, a photo-electrochemical hydrolyzing device and an external circuit, wherein the positive pole of the hydro-generator is connected with a working electrode; the negative pole of the hydro-generator is connected to a counter electrode; the hydro-generator is used for transforming kinetic energy of water flow into electric energy and generating an external electric field; the hydro-generator mainly consists of a water turbine and a propeller; in the photo-electrochemical hydrolyzing device, the working electrode is formed after packaging of a ZnO film which is prepared by a magnetron sputtering method, or is poly-crystal which is 60nm in thickness and grows in a way of ALD (Atomic Layer Deposition) at the temperature of 300 DEG C by adopting a TiO2 film prepared via atomic layer deposition. The reaction device disclosed by the invention is capable of successfully obtaining a photo-electrochemical battery capable of implementing energy transformation by green and reproducible clean energy. The hydro-generator adopted by the reaction device disclosed by the invention is used for transforming mechanical energy into electric energy and is then connected to a photo-anode material in order to efficiently decompose water to generate hydrogen without externally applying bias voltage, so energy consumption is reduced.
Description
Technical field
The invention belongs to clean renewable technical field of new energy utilization, relate to a kind of full green light electrification
Learn the reaction unit of battery (PEC) hydrolytic hydrogen production.
Background technology
Under the overall background that current energy source and environmental problem become increasingly conspicuous, find and clean continuable new energy
Source substitutes traditional fossil energy and is just more and more paid close attention to by people.Among these, Hydrogen Energy is complete with it
The advantage of cleaning burning is in occupation of critical role.Sunlight photocatalysis produces hydrogen and (utilizes quasiconductor to convert light
Hydrogen can be produced for chemical energy) in terms of new energy field, there is good application prospect.At present, directly
Connecing Photocatalyzed Hydrogen Production, i.e. there is gas and is difficult to separate and collection etc. in semiconductor grain Direct Resolution hydrone
Problem.1972, Japanese Scientists A.Fujishima and K.Honda used photoelectrochemical method first
(PEC) utilizing TiO2 to absorb solar energy is hydrogen and oxygen water decomposition, it is proposed that photoelectric decomposition water
The concept of hydrogen manufacturing, has attracted numerous researcher to carry out extensively in-depth study from this.PEC is hydrolyzed into
This low, environmental friendliness, combines the collection of solar energy and the electrolysis of water in a light cell, is can
A kind of Land use systems of lasting new forms of energy.
For photocatalysis hydrogen production catalysis material, water decomposition to be made discharges hydrogen, thermodynamic requirement
As the conduction band current potential of semi-conducting material of catalysis material than hydrogen electeode current potential EH+/H2The most negative, and valency
Band current potential then should be than oxygen electrode current potential EO2/H2O is the most just.Actually due to the existence of kinetics potential barrier,
During Optical Electro-Chemistry hydrogen production by water decomposition, it usually needs electromotive force be greater than the oxidation-reduction potential of water
(1.23V), therefore, in order to make hydrolytic process be smoothed out, it is necessary to an additional bias, and external
The existence of voltage can consume electric energy, causes the waste of the energy.Conventional electrolysis water carrys out hydrogen manufacturing, at present should be
By relatively wide and the method for comparative maturity, but power consumption is big, and required electric energy is to be produced by fossil energy equally
, development potentiality is limited.In terms of Energy harvesting, lose more than gain.So utilizing wind energy, waterpower etc. is clear
It is considered as sustainable development from now on that clean regenerative resource provides applying bias to realize water electrolysis hydrogen production
Preferred approach.
This patent provides the solution of an environmental protection, makes full use of current or tide etc. green
The color energy, is converted into electric energy by hydrogenerator by the kinetic energy of current, is made by the electric energy of above-mentioned acquisition
For PEC electrode, water can be resolved into when without applying bias hydrogen and oxygen efficiently, filling
Divide while make use of clean energy resource, also a saving energy consumption.This Patent equipment is by hydrogenerator, light
Electrochemistry hydrolysis device and connect the two external circuit composition.Its work process is: utilize water wheels to send out
Water flow dynamic energy is converted to electric energy by motor, produces extra electric field, and this extra electric field is connected to work
On electrode, during circuit ON, get final product hydrogen production by water decomposition outside.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, it is provided that a kind of full green light electrochemistry
The reaction unit of battery (PEC) hydrolytic hydrogen production.
The present invention solves the technical scheme that technical problem taked:
The present invention includes hydrogenerator, Optical Electro-Chemistry (PEC) hydrolysis device and is used for connecting water wheels
Electromotor and the external circuit of Optical Electro-Chemistry (PEC) hydrolysis device, wherein the positive pole of hydrogenerator connects work
Making electrode, the negative pole of hydrogenerator is connected on electrode；Described hydrogenerator is by current
Kinetic energy is converted to electric energy, produces extra electric field, is mainly made up of the hydraulic turbine and propeller；Described photoelectricity
Chemistry (PEC) hydrolysis device includes three-electrode system and electrolyte, and wherein three-electrode system includes tool
There are the working electrode of photoelectric respone ability, reference electrode and to electrode；
The described working electrode with photoelectric respone ability is that the ZnO using magnetron sputtering method to prepare is thin
Constitute after film encapsulation, or TiO prepared by employing ald (ALD)2Thin film, thickness 60nm,
The polycrystalline of ALD growth at 300 DEG C；
Described ZnO films deposited by reactive magnetron sputtering is with high pure metal Zn as target, sputters work gas
Pressure 0.3Pa, argon oxygen is than 3:1 (gas flow ratio), and sputter rate is 5.2nm/min, sputtering time
10～30min is adjustable, and the thickness of the ZnO film of gained is 50nm～160nm.
Described reference electrode is saturated calomel electrode.
Described is Pt sheet black for plating Pt to electrode.
Described electrolyte is 0.5M Na2SO4Aqueous solution.
After tested, the hydraulic generator function used in the present invention produces the voltage of 0.6V.The present invention utilizes
Said apparatus carries out full green light electrochemical cell hydrolytic hydrogen production, under the effect of extra electric field, it is achieved
Photocatalytic water.
The invention has the beneficial effects as follows:
The present invention is successfully realized and fully relies on green reproducible clean energy resource and carry out the light of energy conversion
Electrochemical cell.The hydrogenerator that the present invention uses, by being electric energy by changes mechanical energy, reconnects
Go on light anode material, hydrogen can be produced by decomposition water efficiently in the case of without applying bias,
Thus saved energy consumption.
The reaction unit simple in construction of the full green light electrochemical cell hydrolytic hydrogen production of the present invention, saves into
This, it is easy to large-scale production, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is hydrogenerator to be connected to ZnO/FTO device carry out the structure of photocatalytic water performance test
Schematic diagram；
Fig. 2 be unglazed according to time, the I-V curve figure of device when with or without the voltage of external hydrogenerator；
Fig. 3 be unglazed according to time, with or without the efficiency-voltage curve of device during the voltage of external hydrogenerator
Figure；
Fig. 4 be unglazed according to time, with or without the I-t curve chart of device during the voltage of external hydrogenerator；
When Fig. 5 is AM1.5G illumination, with or without the I-V curve of device during the voltage of external hydrogenerator
Figure；
When Fig. 6 is AM1.5G illumination, with or without the efficiency-V of device during the voltage of external hydrogenerator
Curve chart；
When Fig. 7 is AM1.5G illumination, with or without the I-t curve of device during the voltage of external hydrogenerator
Figure；
When Fig. 8 is AM1.5G illumination, with or without the I-t curve of device during the voltage of external hydrogenerator
Figure；
Fig. 9 be unglazed according to time, with or without the I-V curve figure of device during the voltage of external hydrogenerator；
When Figure 10 is AM1.5G illumination, bent with or without the I-V of device during the voltage of external hydrogenerator
Line chart.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further analyzed.
As it is shown in figure 1, apparatus of the present invention include hydrogenerator (1), Optical Electro-Chemistry (PEC) hydrolysis device
(2) and be used for connecting the external circuit of hydrogenerator (1) and Optical Electro-Chemistry (PEC) hydrolysis device (2),
Wherein the positive pole of hydrogenerator connects working electrode, and the negative pole of hydrogenerator is connected on electrode；
Described hydrogenerator (1) is that water flow dynamic energy is converted to electric energy, produces extra electric field, mainly by water
Turbine and propeller composition；Described Optical Electro-Chemistry (PEC) hydrolysis device (2) include three-electrode system,
And electrolyte, wherein three-electrode system includes that the working electrode with photoelectric respone ability (refers to below
For light anode), reference electrode and to electrode；
Embodiment 1:ZnO film thickness 100nm, as light anode after encapsulation, saturated calomel electrode conduct
Reference electrode, Pt sheet is to electrode, and electrolyte solution is the Na of 0.5M2SO4Aqueous solution.As shown in Figure 1.
In PEC test process, compared for the I-V of device during the voltage with or without external hydrogenerator,
I-t and efficiency curve diagram.Fig. 2 be unglazed according to time, device when with or without the voltage of external hydrogenerator
I-V curve figure.When being connected to hydrogenerator, the onset potential of ZnO photo-anode is reduced to by 1.12v
0.93V.Electric current density during 1.5V is brought up to 0.040mA/cm2 by 0.014mA/cm2, improves nearly 3
Times.Fig. 3 be unglazed according to time, when with or without the voltage of external hydrogenerator, the efficiency-voltage of device is bent
Line chart.As seen from the figure, relative to without situation during external hydrogenerator, external water wheels are had to send out
During motor, efficiency improves nearly 3 times.Fig. 4 be unglazed according to time, under 0.5V test with or without external water wheels
The curve chart of the electric current density-time of device during the voltage of electromotor.There is electricity during external hydrogenerator
Current density is 1.784 μ A/cm2, improves closely relative to without electric current density during external hydrogenerator
10 times.When Fig. 5 is AM1.5G illumination, when with or without the voltage of external hydrogenerator, the I-V of device is bent
Line chart.Relative to without electric current density during external hydrogenerator, there is electricity during external hydrogenerator
Current density entirety all has been improved.When Fig. 6 is AM1.5G, when with or without the voltage of external hydrogenerator
The efficiency-voltage curve chart of device.As seen from the figure, relative to without feelings during external hydrogenerator
Condition, when having external hydrogenerator, efficiency improves nearly 3 times.When Fig. 7 is AM1.5G illumination, under 0.5V
The I-t curve chart of device when with or without the voltage of external hydrogenerator of test.There is external hydraulic generator
Electric current density during machine is to improve nearly 1.5 times relative to without electric current density during external hydrogenerator.
Embodiment 2: working electrode is TiO2Thin film, thickness about 60nm, ALD growth at 300 DEG C
Polycrystalline, saturated calomel electrode is as reference electrode, and Pt sheet is to electrode, and electrolyte solution is 0.5M
Na2SO4Aqueous solution.As shown in Figure 1.
In PEC test process, compared for the I-V of device during the voltage with or without external hydrogenerator,
I-t curve chart.When Fig. 8 is AM1.5G illumination, device when with or without the voltage of external hydrogenerator
I-t curve chart.It is 29 μ A/cm2 without electric current density during external hydrogenerator, has outer water receiving
Electric current density during turbine generator is 48 μ A/cm2, electric current density is substantially improved.Fig. 9 is unglazed photograph
Time, the I-V curve figure of device when with or without the voltage of external hydrogenerator.It is connected to hydraulic generator
During machine, the onset potential of TiO2 light anode is reduced to 1.78V by 2.05v, and onset potential is obviously reduced.
When Figure 10 is AM1.5G illumination, the I-V curve of device when with or without the voltage of external hydrogenerator
Figure.As seen from the figure, when having the voltage of external hydrogenerator the photogenerated current of device apparently higher than
Without the situation during voltage of external hydrogenerator.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment,
As long as meeting application claims, belong to protection scope of the present invention.
Claims (1)
1. the reaction unit of a full green light electrochemical cell hydrolytic hydrogen production, it is characterised in that include water wheels
Electromotor, Optical Electro-Chemistry hydrolysis device and being used for connects hydrogenerator and Optical Electro-Chemistry hydrolysis device
External circuit, wherein hydrogenerator positive pole connect working electrode, the negative pole of hydrogenerator is connected to
To on electrode；Described hydrogenerator is that water flow dynamic energy is converted to electric energy, produces extra electric field, mainly
It is made up of the hydraulic turbine and propeller；Described Optical Electro-Chemistry hydrolysis device includes three-electrode system, Yi Ji electricity
Solving liquid, wherein three-electrode system includes having the working electrode of photoelectric respone ability, reference electrode and to electricity
Pole；
The described working electrode with photoelectric respone ability is the ZnO film using magnetron sputtering method to prepare
Constitute after encapsulation, or TiO prepared by employing ald2Thin film, thickness 60nm, at 300 DEG C
The polycrystalline of ALD growth；
Described ZnO films deposited by reactive magnetron sputtering is with high pure metal Zn as target, sputters operating air pressure
0.3Pa, argon carrier of oxygen flow-rate ratio 3:1, sputter rate is 5.2nm/min, sputtering time 10～30min
Adjustable, the thickness of the ZnO film of gained is 50nm～160nm；
Described reference electrode is saturated calomel electrode；
Described is Pt sheet black for plating Pt to electrode；
Described electrolyte is 0.5M Na2SO4Aqueous solution.
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| CN201610210586.3A CN105862061A (en) | 2016-04-05 | 2016-04-05 | Full-green reaction device for hydrolytic hydrogen production of photo-electrochemical battery |
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| CN201610210586.3A CN105862061A (en) | 2016-04-05 | 2016-04-05 | Full-green reaction device for hydrolytic hydrogen production of photo-electrochemical battery |
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Citations (7)
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| CN2670379Y (en) * | 2003-11-17 | 2005-01-12 | 马亮 | Apparatus for preparing hydrogen gas and oxygen by hydroenergy generation |
| CN101376987A (en) * | 2008-09-28 | 2009-03-04 | 大连理工大学 | Photoelectrochemistry composite or coupled hydrogen making and oxygen making apparatus and method |
| CN101608316A (en) * | 2009-07-27 | 2009-12-23 | 新奥科技发展有限公司 | A kind of device for producing hydrogen through decomposing water |
| CN203474901U (en) * | 2013-07-31 | 2014-03-12 | 孙誉宁 | Hydrogen and oxygen production system |
| CN104195588A (en) * | 2014-09-03 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | Method for preparing hydrogen and oxygen by decomposing pure water through photoelectrochemistry |
| CN204385298U (en) * | 2014-12-15 | 2015-06-10 | 天津大学 | Photoelectrocatalysis hydrogen production by water decomposition reaction unit |
| JP2015113240A (en) * | 2013-12-09 | 2015-06-22 | 千代田化工建設株式会社 | Hydrogen production system, hydrogen storage and transportation system provided with the same, and hydrogen production method |
-
2016
- 2016-04-05 CN CN201610210586.3A patent/CN105862061A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2670379Y (en) * | 2003-11-17 | 2005-01-12 | 马亮 | Apparatus for preparing hydrogen gas and oxygen by hydroenergy generation |
| CN101376987A (en) * | 2008-09-28 | 2009-03-04 | 大连理工大学 | Photoelectrochemistry composite or coupled hydrogen making and oxygen making apparatus and method |
| CN101608316A (en) * | 2009-07-27 | 2009-12-23 | 新奥科技发展有限公司 | A kind of device for producing hydrogen through decomposing water |
| CN203474901U (en) * | 2013-07-31 | 2014-03-12 | 孙誉宁 | Hydrogen and oxygen production system |
| JP2015113240A (en) * | 2013-12-09 | 2015-06-22 | 千代田化工建設株式会社 | Hydrogen production system, hydrogen storage and transportation system provided with the same, and hydrogen production method |
| CN104195588A (en) * | 2014-09-03 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | Method for preparing hydrogen and oxygen by decomposing pure water through photoelectrochemistry |
| CN204385298U (en) * | 2014-12-15 | 2015-06-10 | 天津大学 | Photoelectrocatalysis hydrogen production by water decomposition reaction unit |
Non-Patent Citations (1)
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Application publication date: 20160817 |