CN108376613A - It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode - Google Patents
It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode Download PDFInfo
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- CN108376613A CN108376613A CN201810180605.1A CN201810180605A CN108376613A CN 108376613 A CN108376613 A CN 108376613A CN 201810180605 A CN201810180605 A CN 201810180605A CN 108376613 A CN108376613 A CN 108376613A
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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
- H01G9/204—Light-sensitive devices comprising an oxide semiconductor electrode comprising zinc oxides, e.g. ZnO
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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
Abstract
The present invention provides a kind of zno-based composite material and preparation method for dye-sensitized solar cells to electrode.There is excellent stored electrons ability the present invention is based on carbon quantum dot (CQDs) and water-soluble protection can be formed in material surface, ZnO has excellent electron-transporting and C3N4CQDs and C is added in excellent electron transfer3N4Similar conjugated structure can make the surfaces ZnO that are gathered in that the two is stablized form stable three-phase structure, and three's synergistic effect can make I3 ‑Electronic reproduction is quickly obtained on to electrode into I‑, the dye-sensitized solar cells photoelectric conversion efficiency being prepared can reach 9.0%.Ultrasonic pre-reaction so that raw material is evenly dispersed in lower temperature, carries out high pressure hydro-thermal reaction and forms the ZnO C uniformly coated3N4CQDs composite materials.
Description
Technical field
Zno-based technical field of composite preparation of the present invention being used for dye-sensitized solar cells more particularly to one kind
To the zno-based composite material and preparation method of electrode.
Background technology
Dye-sensitized solar cells is mainly made of following components：Light anode, electrolyte and to electrode.To electrode
The important component of dye-sensitized solar cells, effect is transmission electronics and catalytic action, improve the filling of battery because
Son.It is said from mechanism, I3 -Electronic reproduction is obtained on to electrode into I-, the reaction is faster, and photoelectric respone is better.Platinum to electrode by
In its resistance is small and excellent catalytic effect, one layer of platinum is plated on electro-conductive glass at present, can preferably be solved the above problems.But platinum
It is expensive, specific surface area is small, be unfavorable for commercial application, therefore it is excellent to electrode material to find cheap, transmission performance,
It becomes as problem in the urgent need to address.
Carbon quantum dot (CQDs) is the newcomer in carbon nanomaterial family, wide, the anti-light bleachability with absorption spectrum
It is good, non-toxic, be easy to functionalization, can high yield the characteristics such as prepare, be expected to show that it is wide in technical fields such as opto-electronic devices
Wealthy application prospect [Angew.Chem.Int.Ed, 2010,49,6726-6244；Chem.Comm.2012,48.3686-
3705；].Carbon quantum dot is built quantum dot sensitized solar-electricity by the researcher of University of Toronto as photosensitizer
Pond, electricity conversion are only 0.13%；The researcher of indiana university of the U.S. has also made similar work, but its
The needs [NanoLett.2010,10,1869-1873] of practical application are much not achieved in electricity conversion.ZnO is a kind of tool
There are abundance, good environmental stability and there are the semi-conducting materials of a variety of crystal types.However, the pure surfaces ZnO
On active site is less and easy reunion, the recombination rate of electron-hole pair is high, often limits ZnO and exists as a kind of photoelectric material
The application in optical electro-chemistry field.Accordingly, it is desirable to be doped to ZnO, compound improve the photoelectricity of ZnO to build P-N junction
Chemical property.Carbonitride is about 2.7eV as a kind of electron rich organic semiconductor, energy gap, due to its unique electronics energy
Band structure and excellent physicochemical properties so that have huge application prospect in terms of photocatalysis.Consulting literatures are learnt, different
The compound separation of charge efficiency that can improve system is carried out between semiconductor, spread spectrum response range improves catalyst activity.
For example, Wang Xinchen et al. selection semiconductors MoS2With g-C3N4It is compounded to form ultra-thin hetero-junctions, MoS2/g-C3N4The photoproduction electricity of system
Lotus detaches and efficiency of transmission improves；The sub- efficiency of photodissociation aquatic products hydrogen, oxygen-producing amount respectively reaches 2.1% and 1.1% under visible light
(X.C.Wang etal.Angew.Chem.Int.Ed.2013,52 (13), 3621-3625).As far as we know, currently without report
Road design synthesis ZnO-C3N4- CQDs composite materials are simultaneously applied to dye-sensitized solar cells to electrode.
Invention content
The purpose of the present invention is overcoming above-mentioned the deficiencies in the prior art, design, which provides, is used for dye-sensitized solar cells pair
The preparation method of the zno-based composite material of electrode, it is characterised in that：Include the following steps：
Zinc nitrate, CQDs aqueous solutions, melamine and water are uniformly mixed, it is 11 to adjust pH value with ammonium hydroxide, and ultrasound is pre- anti-
Ying Hou is transferred in the reaction kettle of liner tetrafluoroethene and carries out hydro-thermal reaction；After hydro-thermal reaction, washing, drying obtain
ZnO-C3N4- CQDs composite materials
Preferably, the solid-liquid mass ratio of zinc nitrate, CQDs aqueous solutions, melamine and water is 1g：10-15ml：1-4g：
20-30ml, the water-soluble liquid hold-up of carbon quantum dot are 1mg-10mg/ml.
Preferably, the hydro-thermal reaction keeps 1-3h, finally the specific steps are being warming up to 200-200 DEG C with 3-5 DEG C/min
It is cooled to room temperature.
Preferably, the ultrasonic pre-reaction is that the pre-reaction step of ultrasonic 0.5-1.5h is stirred at 90-100 DEG C.
Preferably, the drying condition is to be dried in vacuo 12h at 50 DEG C.
Preferably, the preparation method of the carbon quantum dot be by graphite rod into the water, the continuous electrolysis 120h at 30V,
Through being filtered, washed acquisition.
The present invention also provides a kind of for dye-sensitized solar cells to the zno-based composite material of electrode, described multiple
Condensation material prepares to be formed using the above method.
There is excellent stored electrons ability the present invention is based on CQDs and water-soluble protection can be formed in material surface,
ZnO has excellent electron-transporting and C3N4CQDs and C is added in excellent electron transfer3N4Similar conjugated structure
The surfaces ZnO that are gathered in that the two is stablized can be made to form stable three-phase structure, three's synergistic effect can make I3 -Right
Electronic reproduction is quickly obtained on electrode into I-, electroresponse is excellent, the dye-sensitized solar cells opto-electronic conversion effect being prepared
Rate can reach 9.0%, and preparation method is simple, cheap, have solution processability.In addition, the preparation side of the present invention
Method also has following advantages compared with prior art：
(1) ultrasonic pre-reaction makes the raw materials such as zinc ion, carbon quantum dot, melamine evenly dispersed in lower temperature, shape
At class colloidal reaction raw materials, high pressure hydro-thermal reaction is carried out later, appropriate insulation reaction ultimately forms C3N4- CQDs is uniformly coated
ZnO-C3N4- CQDs composite materials.
(2) hydro-thermal reaction is mild, and the particle size that can ensure that is uniform.
(3) preparation process of the invention is simple, reduces energy consumption, is easy to industrialized production.
Specific implementation mode
Embodiment 1：
It is a kind of for dye-sensitized solar cells to the preparation method of the zno-based composite material of electrode, specific steps are such as
Under：
(1) it is 1g according to solid-liquid mass ratio by zinc nitrate, CQDs aqueous solutions, melamine and water：12ml：2g：25ml is stirred
Mix it is uniformly mixed, with ammonium hydroxide adjust pH value be 11.The water-soluble liquid hold-up of carbon quantum dot is uniformly mixed for 5mg/ml；
(2) mixture in step 1 is stirred to the product after ultrasonic 1h obtains pre-reaction at 95 DEG C；
(3) solution after above-mentioned pre-reaction is transferred in the reaction kettle of liner tetrafluoroethene and carries out hydro-thermal reaction, hydro-thermal
Reaction keeps 2h, is finally cooled to room temperature the specific steps are being warming up to 210 DEG C with 4 DEG C/min；
(4) it washs, be dried in vacuo 12h at 50 DEG C to get ZnO-C3N4- CQDs composite materials.
The preparation method of the carbon quantum dot be by graphite rod into the water, the continuous electrolysis 120h at 30V, through filtering,
What washing obtained.
The preparation of dye-sensitized solar cells：
By ZnO-C3N4- CQDs composite materials are dispersed in isopropanol, form dispersion liquid system uniformly, stable, a concentration of
1mg/mL。
Electro-conductive glass is cleaned up, is then preheating to 90 DEG C, it then will be dissolved with ZnO-C with the method for spraying3N4-CQDs
The dispersion liquid of composite material is coated onto in the electro-conductive glass substrate of preheating, forms thin film, thickness is about 6 microns.By preparation
Electrode is put into vacuum 50 DEG C of dryings 1 hour, prepares dye-sensitized solar cells to electrode.
Electro-conductive glass is pre-processed, is then coated in titania slurry on the electro-conductive glass handled well, high temperature
Immersed in dyestuff after processing and adsorb the working electrode for forming battery overnight, cover on the working electrode (s above-mentioned preparation to electrode,
Two interelectrode gap fillings contain I-/I3 -The electrolyte of redox couple, is prepared into dye-sensitized solar cells.
Solar cell prepared by the above method is tested, open-circuit voltage 0.69V, short circuit current 18.6mA/
cm2, fill factor 0.72, it is 9.0% to obtain photoelectric conversion efficiency.
Embodiment 2：
It is a kind of for dye-sensitized solar cells to the preparation method of the zno-based composite material of electrode, specific steps are such as
Under：
(1) it is 1g according to solid-liquid mass ratio by zinc nitrate, CQDs aqueous solutions, melamine and water：10ml：1g：20ml is stirred
Mix it is uniformly mixed, with ammonium hydroxide adjust pH value be 11.The water-soluble liquid hold-up of carbon quantum dot is uniformly mixed for 1mg/ml；
(2) mixture in step 1 is stirred to the product after ultrasonic 0.5h obtains pre-reaction at 90 DEG C；
(3) solution after above-mentioned pre-reaction is transferred in the reaction kettle of liner tetrafluoroethene and carries out hydro-thermal reaction, hydro-thermal
Reaction keeps 1h, is finally cooled to room temperature the specific steps are being warming up to 200 DEG C with 3 DEG C/min；
(4) it washs, be dried in vacuo 12h at 50 DEG C to get ZnO-C3N4- CQDs composite materials.
The preparation method of the carbon quantum dot be by graphite rod into the water, the continuous electrolysis 120h at 30V, through filtering,
What washing obtained.
It is prepared using the solar cell of embodiment 1 and test method, the open-circuit voltage for obtaining solar cell is
0.69V, short circuit current 16.2mA/cm2, fill factor 0.7, photoelectric conversion efficiency 8.2%.
Embodiment 3：
It is a kind of for dye-sensitized solar cells to the preparation method of the zno-based composite material of electrode, specific steps are such as
Under：
(1) it is 1g according to solid-liquid mass ratio by zinc nitrate, CQDs aqueous solutions, melamine and water：15ml：4g：30ml is stirred
Mix it is uniformly mixed, with ammonium hydroxide adjust pH value be 11.The water-soluble liquid hold-up of carbon quantum dot is uniformly mixed for 10mg/ml；
(2) mixture in step 1 is stirred to the product after ultrasonic 1.5h obtains pre-reaction at 100 DEG C；
(3) solution after above-mentioned pre-reaction is transferred in the reaction kettle of liner tetrafluoroethene and carries out hydro-thermal reaction, hydro-thermal
Reaction keeps 3h, is finally cooled to room temperature the specific steps are being warming up to 220 DEG C with 5 DEG C/min；
(4) it washs, be dried in vacuo 12h at 50 DEG C to get ZnO-C3N4- CQDs composite materials.
The preparation method of the carbon quantum dot be by graphite rod into the water, the continuous electrolysis 120h at 30V, through filtering,
What washing obtained.
Using the solar cell preparation of embodiment 1 and test method, the acquisition solar cell of solar cell is obtained
Open-circuit voltage be 0.68V, short circuit current 15.8mA/cm2, fill factor 0.69, photoelectric conversion efficiency 8.6%.
Embodiment 4：
It is a kind of to be used for preparation method of the dye-sensitized solar cells to the zno-based composite material of electrode, wherein without
Pre-reaction step (2), other steps are same as Example 1.
Using the solar cell preparation of embodiment 1 and test method, the acquisition solar cell of solar cell is obtained
Open-circuit voltage be 0.69V, short circuit current 13.2mA/cm2, fill factor 0.67, photoelectric conversion efficiency 5.8%.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (7)
1. a kind of being used for preparation method of the dye-sensitized solar cells to the zno-based composite material of electrode, it is characterised in that：Packet
Include following steps：
Zinc nitrate, CQDs aqueous solutions, melamine and water are uniformly mixed, it is 11 to adjust pH value with ammonium hydroxide, after ultrasonic pre-reaction,
It is transferred in the reaction kettle of liner tetrafluoroethene and carries out hydro-thermal reaction；After hydro-thermal reaction, washing, drying obtain ZnO-
C3N4- CQDs composite materials.
2. the preparation method of composite material according to claim 1, it is characterised in that：Zinc nitrate, CQDs aqueous solutions, trimerization
The solid-liquid mass ratio of cyanamide and water is 1g：10-15ml：1-4g：20-30ml, the water-soluble liquid hold-up of carbon quantum dot are 1mg-
10mg/ml。
3. the preparation method of composite material according to claim 1, it is characterised in that：The hydro-thermal reaction the specific steps are
It is warming up to 200-200 DEG C with 3-5 DEG C/min, 1-3h is kept, is finally cooled to room temperature.
4. the preparation method of composite material according to claim 1, it is characterised in that：The ultrasound pre-reaction is in 90-
The pre-reaction step of ultrasonic 0.5-1.5h is stirred at 100 DEG C.
5. the preparation method of composite material according to claim 1, it is characterised in that：The drying condition is at 50 DEG C
It is dried in vacuo 12h.
6. the preparation method of composite material according to claim 1, it is characterised in that：The preparation method of the carbon quantum dot
For by graphite rod into the water, the continuous electrolysis 120h at 30V, through being filtered, washed acquisition.
7. a kind of being used for zno-based composite material of the dye-sensitized solar cells to electrode, which is characterized in that use claim
Prepared by 1-6 any one of them methods to form.
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| CN201810180605.1A CN108376613A (en) | 2018-03-05 | 2018-03-05 | It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode |
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| CN201810180605.1A CN108376613A (en) | 2018-03-05 | 2018-03-05 | It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode |
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| CN110124655A (en) * | 2019-05-22 | 2019-08-16 | 天津大学 | A kind of zinc oxide/carbon quantum dot composite photo-catalyst and its preparation method and application |
| CN111490171A (en) * | 2019-05-08 | 2020-08-04 | 广东聚华印刷显示技术有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material |
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| CN106876153A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of electrode of self supporting structure and its preparation and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256327A (en) * | 2018-09-04 | 2019-01-22 | 浙江西溪玻璃有限公司 | A kind of TCO glass and preparation method thereof that Cdot@C3N4 is modified |
| CN111490171A (en) * | 2019-05-08 | 2020-08-04 | 广东聚华印刷显示技术有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material |
| CN110124655A (en) * | 2019-05-22 | 2019-08-16 | 天津大学 | A kind of zinc oxide/carbon quantum dot composite photo-catalyst and its preparation method and application |
| CN110124655B (en) * | 2019-05-22 | 2022-01-25 | 天津大学 | Zinc oxide/carbon quantum dot composite photocatalyst and preparation method and application thereof |
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