CN106783186A - A kind of ZnO nanorod light anode and preparation method thereof, solar cell - Google Patents
A kind of ZnO nanorod light anode and preparation method thereof, solar cell Download PDFInfo
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- CN106783186A CN106783186A CN201611200787.1A CN201611200787A CN106783186A CN 106783186 A CN106783186 A CN 106783186A CN 201611200787 A CN201611200787 A CN 201611200787A CN 106783186 A CN106783186 A CN 106783186A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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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
- 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
Abstract
The invention belongs to optoelectronic pole field, a kind of ZnO nanorod light anode is disclosed, its structure is NiO/CdS/ZnO.The invention also discloses the preparation method of ZnO nanorod light anode, comprise the following steps：S1, ZnO nanorod is prepared by hydro-thermal method；S2, ZnO nanorod surface coat CdS, formed CdS/ZnO structures；S3, NiO is deposited in CdS/ZnO structures, form NiO/CdS/ZnO composite constructions.Nano photoelectric pole of the invention composite, can widen the absorption region to solar spectrum, improve the performance of the optoelectronic pole material for photocatalysis electrolysis water, and preparation method is simple, mainly coats laminated material by spin coating, and cost is relatively low, energy-conserving and environment-protective.
Description
Technical field
The invention belongs to optoelectronic pole field, specifically a kind of ZnO nanorod light anode and preparation method thereof, solar-electricity
Pond.
Background technology
Solar energy is the source of all fossil energies and regenerative resource on the earth, and solar energy is a kind of clean energy resource, can
Regenerate and nonhazardous, in future, solar energy gets a good chance of directly replacing fossil energy.Although nature can be by photosynthetic
Effect stores solar energy in the form of chemical bond, but we need more efficient method and go solution energy crisis to ask
Topic, photochemical catalyzing to have greatly wish makes huge contribution to solve energy crisis, and the method is by using simultaneously
The semi-conducting material that light can be absorbed and energy conversion is carried out carries out the reaction of photochemical catalyzing, finally this most simple with H-H
The form of Hydrochemistry key solar energy is stored.It is easy to quickly be combined yet with photo-generated carrier, causes efficiency also
It is less high.So, we urgently a kind of electrode material can promote the carrier quickly to be passed in solid-solid interface and solid-liquid interface
It is defeated so that material is using can simultaneously keep stability and efficiently capture solar energy.
The semi-conducting material of the photochemical catalyzing for commonly using now all has band gap wider, only in solar spectrum
About 5% ultraviolet-sensitive, therefore the absorption to visible ray is limited, general performance goes out relatively low photoelectric transformation efficiency.
One-component ZnO is a kind of semiconductor material with wide forbidden band for showing excellent characteristic electron, due to depositing for donor level
, the property of N-type semiconductor is shown, and electronics and cavity transmission ability compare TiO2Also to be got well Deng catalysis material.Additionally,
The ZnO material of different nanostructureds has crystallinity and big surface area/volume ratio very high, for example nanometer rods, nanofiber,
Nanotube, nanometer sheet etc., can be applied in photochemical catalyzing reaction.Band gap yet with pure ZnO is too wide, for example
The corresponding band gap wavelengths of 3.37eV are 368nm, are merely able to use a part of ultraviolet light of sunshine, and this inferior position can be
Compensated by being combined with low-gap semiconductor material, it is narrower generally by this energy gaps of CdS（Only 2.4eV）'s
Material modifies wide-band gap material.However, although CdS can be good at absorbing visible ray, the position of band can be also suitably used for continuously not
Disconnected ground is aoxidized and reduction reaction to water, but because it can be subject to serious photoetch, one-component CdS to be not particularly suited for light
Catalytic decomposition water reaction.Due to the S in CdS2-Often prior to water with CdS valence band on photohole occur autoxidation it is anti-
Should, and S2-, SO3 2-, S2O3 2-Plasma is indispensable composition for the CdS materials as photo-catalysis function, and it makes
With being restricted.
The content of the invention
Present invention seek to address that problem above, there is provided a kind of hydrogen production efficiency is high, good stability ZnO nanorod light anode.
It is a further object of the present invention to provide the preparation method of ZnO nanorod light anode.
It is a further object of the present invention to provide the solar cell comprising ZnO nanorod light anode.
To reach one of above-mentioned purpose, the present invention uses following technical scheme：
A kind of ZnO nanorod light anode, its structure is NiO/CdS/ZnO.
The preparation method of above-mentioned ZnO nanorod light anode, comprises the following steps：
S1, ZnO nanorod is prepared by hydro-thermal method；
S2, ZnO nanorod surface coat CdS, formed CdS/ZnO structures；
S3, NiO is deposited in CdS/ZnO structures, form NiO/CdS/ZnO composite constructions.
Further, the step S1 is：The ethanol solution of zinc acetate is spin-coated on ito glass substrate, through for the first time
Ito glass substrate is upside down in the aqueous solution of zinc nitrate and hexa after heating, second heating response is obtained
ZnO nanorod.
Further, the acetic acid zinc concentration is 15 ~ 30mM, and the nitric acid zinc concentration is 70 ~ 90mM, and described six is sub-
The concentration of tetramine is 40 ~ 80mM.
Further, the temperature of the first time heating is 180 ~ 230 DEG C, and the time is 5 ~ 12min；Heat for described second
Temperature be 80 ~ 100 DEG C, the time is 2 ~ 4h.
Further, the step S2 is：The persursor material of CdS is dissolved in the second of cadmium nitrate tetrahydrate and thiocarbamide
In alcoholic solution, and ZnO nanorod surface is spun to, then by ito glass silicon, forms CdS/ZnO structures.
Further, the concentration of the cadmium nitrate tetrahydrate is 0.3 ~ 0.6M, and the concentration of the thiocarbamide is 0.3 ~ 1M.
Further, the step S3 is：Nickel nitrate hexahydrate is dissolved in ethanol solution and prepares NiO presomas,
CdS/ZnO surfaces are spun to, annealing reaction forms NiO layer.
Further, the hexahydrated concentration of the nickel nitrate is 0.2 ~ 0.5M, the temperature of the annealing reaction is 400 ~
500 DEG C, the time is 20 ~ 40 minutes.
ZnO nanorod light anode of the invention can be used for preparing solar cell.
The invention has the advantages that：
The present invention prepares polygon ZnO nanorod by hydro-thermal method, is then coated with ultra-thin CdS layer, is finally deposited on surface again
NiO co-catalysts layer, prepares a kind of nano compound light electrode material of three components（NiO/CdS/ZnO）, this material can carry
Photoelectrochemical behaviour high, is used as light anode catalytic decomposition water efficiency very high.AM 1.5 is used under the low bias voltage effect of -0.6V
Simulated solar light irradiation, the density of photocurrent of generation may be up to 950 μ A/cm2, equivalent to Ag/AgCl 0.5M Na2S and
Na2SO3The effect of solution, density of photocurrent is 6.78 times of the one-component ZnO nanorod for having grown；In the bias voltage of -0.5V
Under effect, density of photocurrent may be up to 530 μ A/cm2, equivalent to Ag/AgCl 1M Na2SO3The effect of solution.
The band gap of the ZnO in the nano compound light electrode material of this three component is larger（3.2eV）, sunshine can only be absorbed
In a part of ultraviolet light, and the energy gap of CdS is narrower（2.4eV）, it is possible to use the visible light part in sunshine, open up
The absorption region to solar spectrum wide.
Transition metal oxide NiO can promote oxidation reaction or capture hole as co-catalyst, improve photocatalysis point
The performance of the optoelectronic pole of Xie Shui.Light induced electron and the compound of hole are repressed in optoelectronic pole material such that it is able to effectively
Quick separating carrier.From fluorescence experiments result, directly on ZnO mix NiO composite torpescence, and compared to
The ZnO material of the one-component for having grown, CdS/ZnO and NiO/CdS/ZnO composites are all relatively active, and carrier can be by
Efficiently quick separating is opened.
NiO/CdS/ZnO nano photoelectrics pole composite can widen the absorption region to solar spectrum, improve for light
The performance of the optoelectronic pole material of catalytic electrolysis water.
Preparation method of the invention is simple, mainly coats laminated material by spin coating, and cost is relatively low, the middle temperature of preparation process
Spend relatively low, energy-conserving and environment-protective.
Brief description of the drawings
Fig. 1 is the structural representation of the ZnO nanorod light anode of embodiment 1；
Fig. 2 is the SEM figures of each material of embodiment 1；
Fig. 3 is the fluorescence spectra of each one-component material of embodiment 1；
Fig. 4 is the fluorescence spectra of each composite of embodiment 1；
Fig. 5 is the current density-potential curve of each material of embodiment 1；
Fig. 6 is the current density-time graph of the solar cell of embodiment 1；
Fig. 7 is the hydrogen production rate curve of the solar cell of embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
ZnO nanorod light anode is prepared according to following steps：
S1, growing ZnO nanorod
Zinc acetate is dissolved in ethanol solution be made concentration be 20mM ZnO seed presomas, at ambient temperature with
The rotating speed of 2000rpm. spin coating 30s on ito glass substrate, ito glass substrate is placed in 180 ~ 230 DEG C of heating plate and is added
5 ~ 12min of heat, then turn around to be suspended at and fill zinc nitrate（75mM）And hexa（50mM）The aqueous solution reactor
In ware, 90 DEG C of heating responses are removed after 3 hours from growth-promoting media, are dried after being rinsed with ethanol and deionization, obtain ZnO nano
Rod.
The growth of S2, CdS coat
The persursor material of CdS is dissolved in cadmium nitrate tetrahydrate（0.5M）And thiocarbamide（0.5M）Ethanol solution in, in ring
Substrate is placed in 90 DEG C of heating plate and is heated in ZnO nanorod surface spin coating 30s with the rotating speed of 2000rpm. at a temperature of border
Until forming one layer of film of very thin yellow, CdS is coated with ZnO nanorod as Shell Materials, finally with ethanol and go from
Son makees drying and processing after rinsing, form CdS/ZnO structures.
S3, prepare NiO layer
Nickel nitrate hexahydrate is dissolved in ethanol solution be made concentration be 0.3M NiO presomas, at ambient temperature with
Sample is finally sent into tube furnace 450 DEG C of annealing under ar gas environment by the rotating speed of 2000rpm. in CdS/ZnO surfaces spin coating 30s
30 minutes, form one layer of very thin fine and close NiO layer.
Fig. 1 is the structural representation of ZnO nanorod light anode；Fig. 2 a are ZnO nanorods, and Fig. 2 b are CdS coats, Fig. 2 c
It is NiO catalyst layers, Fig. 2 d are the cross sections of optoelectronic pole material.
Fig. 3 is the fluorescence spectra of NiO, CdS, ZnO, and Fig. 4 is the glimmering of NiO/ZnO, ZnO, CdS/ZnO, NiO/CdS/ZnO
Light spectrogram, it is known that, light induced electron and the compound of hole are repressed in NiO/CdS/ZnO such that it is able to effectively fast
Speed separates carrier.
Fig. 5 is the current density-potential curve of each material of embodiment 1, and electric current-bias voltage characteristic curve is in 0.25M
Na2S and 0.35M Na2SO3Solution, with what is determined under the irradiation of AM1.5 simulated solar irradiations, ZnO nanorod light anode is with electricity
The response of the variable-current of pressure is the most obvious.With the simulated solar light irradiation of AM 1.5 under the low bias voltage effect of -0.6V,
The density of photocurrent of generation may be up to 950 μ A/cm2, equivalent to Ag/AgCl 0.5M Na2S and Na2SO3The effect of solution, light
Current density is 6.78 times of the one-component ZnO nanorod for having grown；Under the bias voltage effect of -0.5V, density of photocurrent
Up to 530 μ A/cm2, equivalent to Ag/AgCl 1M Na2SO3The effect of solution.
Fig. 6 is the current density-time graph of the solar cell being made of ZnO nanorod light anode, over time
Change, the photocatalysis performance stabilization of device.
Fig. 7 is the hydrogen production rate curve of the solar cell being made of ZnO nanorod light anode, is illustrated in 10 hours,
The hydrogen production rate of unit area is very stable.Current density-time graph and hydrogen production rate are all the Na in 0.25M2S and
0.35M Na2SO3Solution, with what is determined under the irradiation of AM1.5 simulated solar irradiations.
Embodiment 2
ZnO nanorod light anode is prepared according to following steps：
S1, growing ZnO nanorod
Zinc acetate is dissolved in ethanol solution be made concentration be 15mM ZnO seed presomas, at ambient temperature with
The rotating speed of 2000rpm. spin coating 30s on ito glass substrate, ito glass substrate is placed in 180 DEG C of heating plate and is heated
12min, then turn around to be suspended at and fill zinc nitrate（70mM）And hexa（60mM）The aqueous solution reaction vessels in,
100 DEG C of heating responses are removed after 2 hours from growth-promoting media, are dried after being rinsed with ethanol and deionization, obtain ZnO nanorod.
The growth of S2, CdS coat
The persursor material of CdS is dissolved in cadmium nitrate tetrahydrate（0.3M）And thiocarbamide（1M）Ethanol solution in, in environment
At a temperature of with the rotating speed of 2000rpm. in ZnO nanorod surface spin coating 30s, substrate is placed in 90 DEG C of heating plate heat it is straight
To one layer of film of very thin yellow is formed, CdS is coated with ZnO nanorod as Shell Materials, finally with ethanol and deionization
Make drying and processing after flushing, form CdS/ZnO structures.
S3, prepare NiO layer
Nickel nitrate hexahydrate is dissolved in ethanol solution be made concentration be 0.5M NiO presomas, at ambient temperature with
Sample is finally sent into tube furnace 400 DEG C of annealing under ar gas environment by the rotating speed of 2000rpm. in CdS/ZnO surfaces spin coating 30s
40 minutes, form one layer of very thin fine and close NiO layer.
Embodiment 3
ZnO nanorod light anode is prepared according to following steps：
S1, growing ZnO nanorod
Zinc acetate is dissolved in ethanol solution be made concentration be 30mM ZnO seed presomas, at ambient temperature with
The rotating speed of 2000rpm. spin coating 30s on ito glass substrate, ito glass substrate is placed in 220 DEG C of heating plate and is heated
6min, then turn around to be suspended at and fill zinc nitrate（90mM）And hexa（80mM）The aqueous solution reaction vessels in,
82 DEG C of heating responses are removed after 4 hours from growth-promoting media, are dried after being rinsed with ethanol and deionization, obtain ZnO nanorod.
The growth of S2, CdS coat
The persursor material of CdS is dissolved in cadmium nitrate tetrahydrate（0.6M）And thiocarbamide（0.3M）Ethanol solution in, in ring
Substrate is placed in 90 DEG C of heating plate and is heated in ZnO nanorod surface spin coating 30s with the rotating speed of 2000rpm. at a temperature of border
Until forming one layer of film of very thin yellow, CdS is coated with ZnO nanorod as Shell Materials, finally with ethanol and go from
Son makees drying and processing after rinsing, form CdS/ZnO structures.
S3, prepare NiO layer
Nickel nitrate hexahydrate is dissolved in ethanol solution be made concentration be 0.2M NiO presomas, at ambient temperature with
Sample is finally sent into tube furnace 500 DEG C of annealing under ar gas environment by the rotating speed of 2000rpm. in CdS/ZnO surfaces spin coating 30s
20 minutes, form one layer of very thin fine and close NiO layer.
The above, specific embodiment only of the invention, but protection scope of the present invention is not limited thereto, and it is any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (10)
1. a kind of ZnO nanorod light anode, it is characterised in that its structure is NiO/CdS/ZnO.
2. the preparation method of ZnO nanorod light anode according to claim 1, it is characterised in that comprise the following steps：
S1, ZnO nanorod is prepared by hydro-thermal method；
S2, ZnO nanorod surface coat CdS, formed CdS/ZnO structures；
S3, NiO is deposited in CdS/ZnO structures, form NiO/CdS/ZnO composite constructions.
3. preparation method according to claim 2, it is characterised in that the step S1 is：By the ethanol solution of zinc acetate
It is spin-coated on ito glass substrate, ito glass substrate is upside down in the water of zinc nitrate and hexa after being heated through first time
In solution, second heating response obtains ZnO nanorod.
4. preparation method according to claim 3, it is characterised in that the acetic acid zinc concentration is 15 ~ 30mM, the nitre
Sour zinc concentration is 70 ~ 90mM, and the concentration of the hexa is 40 ~ 80mM.
5. preparation method according to claim 3, it is characterised in that the temperature of the first time heating is 180 ~ 230 DEG C,
Time is 5 ~ 12min；The temperature of second heating is 80 ~ 100 DEG C, and the time is 2 ~ 4h.
6. preparation method according to claim 2, it is characterised in that the step S2 is：The persursor material of CdS is molten
Solution is spun to ZnO nanorod surface in the ethanol solution of cadmium nitrate tetrahydrate and thiocarbamide, then ito glass substrate is added
Heat, forms CdS/ZnO structures.
7. preparation method according to claim 6, it is characterised in that the concentration of the cadmium nitrate tetrahydrate is 0.3 ~
0.6M, the concentration of the thiocarbamide is 0.3 ~ 1M.
8. preparation method according to claim 2, it is characterised in that the step S3 is：Nickel nitrate hexahydrate is molten
Solution prepares NiO presomas in ethanol solution, is spun to CdS/ZnO surfaces, and annealing reaction forms NiO layer.
9. preparation method according to claim 8, it is characterised in that the hexahydrated concentration of nickel nitrate is 0.2 ~
0.5M, the temperature of the annealing reaction is 400 ~ 500 DEG C, and the time is 20 ~ 40 minutes.
10. a kind of solar cell, it is characterised in that it includes the ZnO nanorod light anode described in claim 1.
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| CN109244440A (en) * | 2018-11-30 | 2019-01-18 | 深圳大学 | A kind of NiO-ZnO composite material and preparation method and lithium ion battery |
| CN113281390A (en) * | 2021-07-02 | 2021-08-20 | 萍乡学院 | BiSeTe/CdS nano-rod material, photo-anode, preparation method and Cu thereof2+Applications on detection |
| EP3988208A4 (en) * | 2019-06-19 | 2023-08-02 | Universitat de Valéncia | Catalytic nickel oxide sheet, method for obtaining it and use thereof |
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Application publication date: 20170531 |