CN109326445A - Nano-composite counter electrode and preparation method for quantum dot sensitized solar battery - Google Patents
Nano-composite counter electrode and preparation method for quantum dot sensitized solar battery Download PDFInfo
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- CN109326445A CN109326445A CN201811373717.5A CN201811373717A CN109326445A CN 109326445 A CN109326445 A CN 109326445A CN 201811373717 A CN201811373717 A CN 201811373717A CN 109326445 A CN109326445 A CN 109326445A
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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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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 nano-composite counter electrode and preparation method thereof that the invention discloses a kind of for quantum dot sensitized solar battery, including ZnO nano-rod array and in CoS the or CuS nano particle of ZnO nanorod surface deposition.The ZnO nanorod that high-sequential arranges in the present invention has high conductivity, is conducive to quickly for the electronics in external circuit to be transferred to the position CoS, CuS with high catalytic activity, promotes to the electron-transport between electrode and electrolyte.Electrode is prepared by whole soln method for composite nanostructure of the present invention, simple process, it is low in cost, have excellent performance, as QDSSC to electrode, under identical experiment condition, ZnO/CuS and ZnO/CoS improve 141% and 86% than photoelectric conversion efficiency of traditional Pt to the battery of electrode assembling respectively to the photoelectric conversion efficiency of the battery of electrode assembling.
Description
Technical field
The invention belongs to field of solar energy utilization, also belong to field of nanometer material technology, and in particular to one kind is quick for quantum dot
Change the nano composite structure of solar battery to electrode and preparation method thereof.
Background technique
The bring Heavy environmental pollution in the increasingly exhausted and its use process of fossil energy, it is inexhaustible with it not
The solar energy exhausted is at important countermeasure to solve this problem.In all kinds of novel solar batteries, preparation process is simple, cost
Cheap quantum dot sensitized solar battery (QDSSC) causes the extensive concern of researcher.Compared with dye sensitizing agent, amount
Son point has adjustable band structure, and higher extinction coefficient, biggish natural dipole moment and more exciton regeneration efficities etc. are unique
The advantages of (A.Kongkanand, et al., J.Am.Chem.Soc., 130 (2008), 4007).Therefore, research QDSSC is split
Hair low cost, efficient solar battery have very important significance.
QDSSC is mainly formed by the light anode of absorption quantum dot, electrolyte and to electrode three parts, wherein to the work of electrode
With being that the electron transmission of external circuit is made its reducing/regenerating to electrolyte.In addition, oxidation in electrolyte can also be accelerated to go back electrode
Original plays catalytic action to the electron exchange rate between cathode.In dye-sensitized cell common Pt to electrode not only at
This height, and the S in more sulphur electrolyte2-It is easily absorbing the surface Pt, generation poisons effect, reduces catalysis of the Pt to electrolyte
Performance (J.G.Radich, et al., J.Phys.Chem.Lett., 2 (2011), 2453), to seriously affect the filling of battery
The factor, this is also a major reason for causing QDSSC photoelectric conversion efficiency relatively low, so, Pt is not to be suitable for QDSSC
It is optimal to electrode material.In order to improve the electron transfer rate to electrode/electrolyte interface, multiple material is attempted as to electricity
Pole is used in QDSSC, such as CuS (A.D.Savariraj, et al., Electrochim.Acta, 149 (2014), 364),
PbS(Tachan.Z,et al.,J.Phys.Chem.C,115(2011),6162)、CoS(Yuan.H,et al.,
J.Electrochem.Soc., 160 (2013), H624) etc., although these types overcomes cost and active two sides to electrode material
The problem of face, but metal sulfide to the electrode overwhelming majority is obtained by corrosion metal foil at present, is not only difficult to seal
It fills, and be packaged into the later electrolyte of battery can continuously corrode metal foil, causes the stability of battery very poor, be difficult
Reach practical purpose.Composite nanostructure in the present invention combines the advantage of two kinds of nano materials to electrode, be QDSSC not
Carry out the development trend to electrode material, existing article reports CuS-C (L.Li, et al., J.Phys.Chem.C, 118 at present
(2014), 16526) have with ITO/CuS (Y.Jiang, et al., Nano Lett., 14 (2014), 365) nucleocapsid array etc.
High-specific surface area and the nanocomposite of conductivity obtain encouraging result of study to electrode.
Summary of the invention
The object of the present invention is to provide a kind of nanocomposites of whole soln method preparation to electrode, will have high conductivity
It is combined with the ZnO nano-rod array of large specific surface area with CoS, CuS catalyst with high catalytic activity, by playing two
The collaboration advantage of person forms the composite nanostructure of a kind of high-performance, low cost to electrode, to solve existing QDSSC to electricity
Problem extremely at high cost, catalytic performance is low, stability is poor.
To achieve the above object, the present invention provides following schemes:
Nano-composite counter electrode for quantum dot sensitized solar battery includes ZnO nano-rod array and in ZnO nano
The composite nano metal sulfide particle of stick array surface deposition.
Preferably, the composite nano metal sulfide particle includes CoS nano particle.
Preferably, the composite nano metal sulfide particle includes CuS nano particle.
Preferably, the ZnO nano-rod array preparation method the following steps are included:
(1) preparation of ZnO seed layer
It is the precursor of ZnO with zinc acetate, using ethylene glycol monomethyl ether as solvent, using monoethanolamine as stabilizer, three's mixing
It is stirred to react at 60 DEG C afterwards 30 minutes, is then aged 24 hours at a constant temperature and forms uniform ZnO precursor colloidal sol, then will
It is spun on the electro-conductive glass substrate surface cleaned up, is put into Muffle furnace, is heat-treated at 200 DEG C 15 minutes thin to solidify
Film repeats above-mentioned spin coating and heat treatment process 2~5 times, is finally putting into Muffle furnace, in 350 DEG C of annealing, 1 hour formation ZnO seed
Crystal layer；
(2) growth of ZnO nano-rod array
ZnO nano-rod array is prepared using cryochemistry bath sedimentation, growth solution is isometric zinc nitrate aqueous solution
With the mixed liquor of sodium hydrate aqueous solution, mixed liquor stir 1 hour after, tiltedly downward by the ZnO seed layer substrate front surface prepared
It is suspended in growth solution, then the beaker for filling growth-promoting media is placed in thermostat water bath, 30~60 are grown in 83 DEG C of water-baths
Minute forms ZnO nano-rod array, is rinsed well after taking-up with deionized water and ethyl alcohol, is placed in 200 DEG C of Muffle furnace and does
It is dry, it is spare.
Preferably, the concentration of zinc acetate solution described in step (1) is 0.1~0.8mol/L, zinc acetate and monoethanolamine
Molar ratio be 1:1；The concentration of zinc nitrate solution is 0.08mol/L in ZnO growth-promoting media described in step (2), and sodium hydroxide is molten
The concentration of liquid is 1.8mol/L, and the diameter of the ZnO nanorod of preparation is 80~150nm, and length is 1~3 μm.
Preferably, the electro-conductive glass substrate is FTO glass or ito glass, and revolving speed when spin coating ZnO colloidal sol is 3000
~4000 revs/min, the time be 30 seconds.
The present invention also provides the preparation methods of the nano-composite counter electrode for quantum dot sensitized solar battery, including with
Lower step:
CoS nano particle, the ZnO that will be prepared are deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method
Nanometer stick array immerses in cobalt acetate aqueous solution 1 minute, makes Co2+It is adsorbed on the surface ZnO, is then rinsed with deionized water；Again will
It is placed in sodium sulfide solution 1 minute, makes Co2+With S2-The CoS nano particle that reaction is formed is adsorbed on the surface ZnO, uses again
Deionized water is rinsed；Above procedure is a SILAR circulation.
Preferably, CuS nano particle is deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method, will prepared
Good ZnO nano-rod array immerses in acetic acid copper liquor 1 minute, makes Cu2+It is adsorbed on the surface ZnO, is then rushed with deionized water
It washes；It is placed it in sodium sulfide solution again 1 minute, makes Cu2+With S2-The CuS nano particle that reaction is formed is adsorbed on ZnO table
Face is rinsed with deionized water again；Above procedure is a SILAR circulation.
Preferably, the cobalt acetate/acetic acid copper liquor concentration is 0.05~0.1mol/L, deposition SILAR circulation
Number is 3~12 times.
The invention discloses following technical effects:
With it is existing to electrode material compared with, composite nanostructure nanometer stick array prepared by the present invention to electrode have it is following
Advantage:
(1) in the present invention, ZnO plays the role of supporting catalyst and transmits electronics, and ZnO nano-rod array has big ratio
Surface area can load more CoS, CuS catalyst, improve the contact area of catalyst and electrolyte, significantly reduce electrolysis
Liquid/to the transmission resistance of electrode interface.
(2) ZnO nanorod of high-sequential arrangement has high conductivity, is conducive to quickly pass the electronics in external circuit
It is defeated to arrive the position CoS, CuS with high catalytic activity, promote to the electron-transport between electrode and electrolyte；Simultaneously because nanometer
Gap between stick array is bigger, and electrolyte can be made smoothly to penetrate into the ZnO nanorod that load has metal sulfide catalyst
Between, it may advantageously facilitate S2-/Sn2-Fast reaction between redox couple.
(3) electrode is prepared by whole soln method for composite nanostructure, simple process, it is low in cost, have excellent performance,
As QDSSC to electrode, under identical experiment condition, ZnO/CuS and ZnO/CoS turn the photoelectricity of the battery of electrode assembling
It changes efficiency and improves 141% and 86% than photoelectric conversion efficiency of traditional Pt to the battery of electrode assembling respectively.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is scanning electron microscope (SEM) photo of ZnO nano-rod array, and (a) is section SEM figure, (b) is surface
SEM figure；
Fig. 2 is that the nano composite structure of ZnO nano-rod array load C oS catalyst prepared by embodiment 1 sweeps electrode
Retouch electron microscope picture；
Fig. 3 is that the nano composite structure of ZnO nano-rod array loaded Cu S catalyst prepared by embodiment 2 sweeps electrode
Retouch electron microscope picture；
Fig. 4 is QDSSC current -voltage curve figure of the nano composite structure to electrode assembling of embodiment 1-2 preparation.
Fig. 5 is comparative example tradition Pt to electrode and TiO2The current -voltage curve figure of/CdSe light anode institute assembled battery.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
Embodiment 1
(1) ZnO nano-rod array load C oS catalyst nano composite construction is prepared to electrode
(1) preparation of ZnO seed layer: using ethylene glycol monomethyl ether as solvent, and zinc acetate dissolution is wherein configured to concentration
For the solution of 0.3mol/L, it then is added drop-wise to above-mentioned solution using the monoethanolamine of same molar ratio as stabilizer, is prepared
Mixed liquor in 60 DEG C of water-bath heating stirring 30 minutes, obtain colloidal sol after being finally aged 24 hours in 30 DEG C of insulating box
Spin coating liquid.Then use revolving speed for 3000 revs/min, the time is that colloidal sol is spun on the FTO glass cleaned up by 30 seconds technique
On glass, it is put into 200 DEG C of Muffle furnace and anneals 15 minutes with cured film.Above-mentioned spin coating and annealing process is repeated twice it
Afterwards, it is put into Muffle furnace and gradually rises to 350 DEG C with 5 DEG C/min of rate, and anneal 30 minutes at this temperature, colloidal sol divides completely
Crystallization forms ZnO seed crystal layer film after solution.
(2) it uses cryochemistry to bathe sedimentation growing ZnO nanorod arrays: preparing 50ml concentration respectively first as 0.08mol/
The zinc nitrate aqueous solution and 50ml concentration of L is the sodium hydrate aqueous solution of 1.8mol/L, by zinc nitrate solution after stirring evenly
Slowly to sodium hydroxide solution is entered, after mixed liquor stirs 1 hour, by the oblique court of ZnO seed layer substrate front surface well prepared in advance
Under be suspended in growth solution, and grow 30 minutes in 80 DEG C of thermostat water bath, take out receiving of having grown after reaction
Rice rod array film, is rinsed well with deionized water and ethyl alcohol, and be dried for standby in 200 DEG C of Muffle furnace respectively.
(3) CoS catalysis material nano particle is deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method: will
The ZnO nano-rod array prepared immerses in 0.1mol/L cobalt acetate aqueous solution 1 minute, makes Co2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in 0.1mol/L sodium sulfide solution again 1 minute, Co2+With S2-Reaction forms CoS nanometers
Granular absorption is rinsed with deionized water again on the surface ZnO.Above procedure is a SILAR circulation, repeats the circulation 9 times systems
It is standby to obtain ZnO nano-rod array load C oS to electrode.
(2) the porous TiO of preparation CdSe quantum dot sensitization2Light anode (TiO2/CdSe)
By silk screen print method by Dyesol-18NRT TiO2Slurry is coated on FTO electro-conductive glass, then at 500 DEG C
Muffle furnace in anneal 30 minutes, be cooled to room temperature to be formed with a thickness of 10 μm, area is 5 × 5mm2Porous TiO2Electrode.Then
Using electrochemical deposition method (X.Song, et al., Electrochimica Acta, 2013,108,449) in porous TiO2 table
Face deposits CdSe quantum dot, forms TiO2/ CdSe electrode.
(3) it assembling quantum dot sensitization solar battery and tests
The TiO that will be prepared2/ CdSe light anode is placed on table top, and the heat-sealing film frame cut (50 μm) is stacked
In above-mentioned electrode surrounding, then ZnO nano-rod array load C oS nano composite structure uses electrode in heat-sealing film surface cover
By pouring into more sulphur electrolyte (1mol/L Na to the aperture accomplished fluently in advance on electrode after heat sealing machine heating encapsulation2S and 1mol/L
The aqueous solution of S powder), then the preparation of quantum dot sensitized solar battery can be completed in sealed aperture.Assembled battery exists
100mW/cm2Current -voltage curve is tested under the simulated solar irradiation of (AM 1.5).
Embodiment 2
(1) ZnO nano-rod array loaded Cu S catalyst nano composite construction is prepared to electrode
(1) preparation of ZnO seed layer: with embodiment 1.
(2) sedimentation growing ZnO nanorod arrays are bathed using cryochemistry: with embodiment 1.
(3) CuS catalysis material nano particle is deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method: will
The ZnO nano-rod array prepared immerses in 0.1mol/L acetic acid copper liquor 1 minute, makes Cu2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in 0.1mol/L sodium sulfide solution again 1 minute, Cu2+With S2-The CuS that reaction is formed receives
Rice grain is adsorbed on the surface ZnO, is rinsed again with deionized water.Above procedure is a SILAR circulation, is repeated the circulation 10 times
ZnO nano-rod array loaded Cu S is prepared to electrode.
(2) the porous TiO of preparation CdSe quantum dot sensitization2Light anode (TiO2/CdSe)
By silk screen print method by Dyesol-18NRT TiO2Slurry is coated on FTO electro-conductive glass, then at 500 DEG C
Muffle furnace in anneal 30 minutes, be cooled to room temperature to be formed with a thickness of 10 μm, area is 5 × 5mm2Porous TiO2Electrode.Then
Using electrochemical deposition method (X.Song, et al., Electrochimica Acta, 2013,108,449) in porous TiO2 table
Face deposits CdSe quantum dot, forms TiO2/ CdSe electrode.
(3) it assembling quantum dot sensitization solar battery and tests
The TiO that will be prepared2/ CdSe light anode is placed on table top, and the heat-sealing film frame cut (50 μm) is stacked
In above-mentioned electrode surrounding, then ZnO nano-rod array loaded Cu S nano composite structure uses electrode in heat-sealing film surface cover
By pouring into more sulphur electrolyte (1mol/L Na to the aperture accomplished fluently in advance on electrode after heat sealing machine heating encapsulation2S and 1mol/L
The aqueous solution of S powder), then the preparation of quantum dot sensitized solar battery can be completed in sealed aperture.Assembled battery exists
100mW/cm2Current -voltage curve is tested under the simulated solar irradiation of (AM 1.5).
Embodiment 3
(1) ZnO nano-rod array load C oS catalyst nano composite construction is prepared to electrode
(1) preparation of ZnO seed layer: using ethylene glycol monomethyl ether as solvent, and zinc acetate dissolution is wherein configured to concentration
For the solution of 0.8mol/L, it then is added drop-wise to above-mentioned solution using the monoethanolamine of same molar ratio as stabilizer, is prepared
Mixed liquor in 60 DEG C of water-bath heating stirring 30 minutes, obtain colloidal sol after being finally aged 24 hours in 30 DEG C of insulating box
Spin coating liquid.Then use revolving speed for 4000 revs/min, the time is that colloidal sol is spun on the ITO glass cleaned up by 30 seconds technique
On glass, it is put into 200 DEG C of Muffle furnace and anneals 15 minutes with cured film.Above-mentioned spin coating and annealing process is repeated twice it
Afterwards, it is put into Muffle furnace and gradually rises to 350 DEG C with 5 DEG C/min of rate, and anneal 30 minutes at this temperature, colloidal sol divides completely
Crystallization forms ZnO seed crystal layer film after solution.
(2) sedimentation growing ZnO nanorod arrays are bathed using cryochemistry: with embodiment 1.
(3) CoS catalysis material nano particle is deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method: will
The ZnO nano-rod array prepared immerses in 0.05mol/L acetic acid copper liquor 1 minute, makes Co2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in 0.1mol/L sodium sulfide solution again 1 minute, Cu2+With S2-The CuS that reaction is formed receives
Rice grain is adsorbed on the surface ZnO, is rinsed again with deionized water.Above procedure is a SILAR circulation, is repeated the circulation 12 times
ZnO nano-rod array load C oS is prepared to electrode.
(2) the porous TiO of preparation CdSe quantum dot sensitization2Light anode (TiO2/CdSe)
By silk screen print method by Dyesol-18NRT TiO2Slurry is coated on ITO electro-conductive glass, then at 500 DEG C
Muffle furnace in anneal 30 minutes, be cooled to room temperature to be formed with a thickness of 10 μm, area is 5 × 5mm2Porous TiO2Electrode.Then
Using electrochemical deposition method (X.Song, et al., Electrochimica Acta, 2013,108,449) in porous TiO2 table
Face deposits CdSe quantum dot, forms TiO2/ CdSe electrode.
(3) it assembling quantum dot sensitization solar battery and tests
The TiO that will be prepared2/ CdSe light anode is placed on table top, and the heat-sealing film frame cut (50 μm) is stacked
In above-mentioned electrode surrounding, then ZnO nano-rod array load C oS nano composite structure uses electrode in heat-sealing film surface cover
By pouring into more sulphur electrolyte (1mol/L Na to the aperture accomplished fluently in advance on electrode after heat sealing machine heating encapsulation2S and 1mol/L
The aqueous solution of S powder), then the preparation of quantum dot sensitized solar battery can be completed in sealed aperture.
Embodiment 4
(1) ZnO nano-rod array loaded Cu S catalyst nano composite construction is prepared to electrode
(1) preparation of ZnO seed layer: with embodiment 3.
(2) sedimentation growing ZnO nanorod arrays are bathed using cryochemistry: with embodiment 1.
(3) CuS catalysis material nano particle is deposited on ZnO nanorod surface using layer-by-layer ionic adsorption and reaction method: will
The ZnO nano-rod array prepared immerses in 0.1mol/L acetic acid copper liquor 1 minute, makes Cu2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in 0.1mol/L sodium sulfide solution again 1 minute, Cu2+With S2-The CuS that reaction is formed receives
Rice grain is adsorbed on the surface ZnO, is rinsed again with deionized water.Above procedure is a SILAR circulation, is repeated the circulation 8 times
ZnO nano-rod array loaded Cu S is prepared to electrode.
(2) the porous TiO of preparation CdSe quantum dot sensitization2Light anode (TiO2/CdSe)
By silk screen print method by Dyesol-18NRT TiO2Slurry is coated on ITO electro-conductive glass, then at 500 DEG C
Muffle furnace in anneal 30 minutes, be cooled to room temperature to be formed with a thickness of 10 μm, area is 5 × 5mm2Porous TiO2Electrode.Then
Using electrochemical deposition method (X.Song, et al., Electrochimica Acta, 2013,108,449) in porous TiO2 table
Face deposits CdSe quantum dot, forms TiO2/ CdSe electrode.
(3) it assembling quantum dot sensitization solar battery and tests
The TiO that will be prepared2/ CdSe light anode is placed on table top, and the heat-sealing film frame cut (50 μm) is stacked
In above-mentioned electrode surrounding, then ZnO nano-rod array loaded Cu S nano composite structure uses electrode in heat-sealing film surface cover
By pouring into more sulphur electrolyte (1mol/L Na to the aperture accomplished fluently in advance on electrode after heat sealing machine heating encapsulation2S and 1mol/L
The aqueous solution of S powder), then the preparation of quantum dot sensitized solar battery can be completed in sealed aperture.
Comparative example
(1) the porous TiO of preparation CdSe quantum dot sensitization2Light anode (TiO2/CdSe)
By silk screen print method by Dyesol-18NRT TiO2Slurry is coated on ITO electro-conductive glass, then at 500 DEG C
Muffle furnace in anneal 30 minutes, be cooled to room temperature to be formed with a thickness of 10 μm, area is 5 × 5mm2Porous TiO2Electrode.Then
Using electrochemical deposition method (X.Song, et al., Electrochimica Acta, 2013,108,449) in porous TiO2 table
Face deposits CdSe quantum dot, forms TiO2/ CdSe electrode.
(2) it assembling quantum dot sensitization solar battery and tests
The TiO that will be prepared2/ CdSe light anode is placed on table top, and the heat-sealing film frame cut (50 μm) is stacked
In above-mentioned electrode surrounding, then tradition Pt is to electrode in heat-sealing film surface cover, by electrode after being encapsulated with heat sealing machine heating
On the aperture accomplished fluently in advance pour into more sulphur electrolyte (1mol/L Na2The aqueous solution of S and 1mol/L S powder), then sealed aperture
The preparation of quantum dot sensitized solar battery can be completed.Assembled battery is in 100mW/cm2The simulated solar of (AM 1.5)
Current -voltage curve is tested under light.
Fig. 1 (a) is the section SEM figure of ZnO nano-rod array, as we can see from the figure the vertical FTO substrate orientation of nanometer rods
Growth, orientation height is consistent, is in array format, and discrete orderly between stick and stick.The length of nanometer rods is about 2 μm.Fig. 1
It (b) is ZnO nano-rod array surface SEM figure, as can be seen from the figure nanometer rods are closely evenly distributed, the diameter distribution of nanometer rods
Uniformly, about 50nm.
Fig. 2 is that ZnO nano array load C oS catalyst nano composite construction schemes the surface SEM of electrode, ZnO nanorod
Surface deposited some CoS nano particles, such a construction increases to electrode and electrolyte contacts area, to help to improve
To the catalytic activity of electrode.
Fig. 3 is that ZnO nano array loaded Cu S catalyst nano composite construction schemes the surface SEM of electrode, ZnO nanorod
Surface deposited some CuS nano particles, such a construction increases to electrode and electrolyte contacts area, to help to improve
To the catalytic activity of electrode.
Fig. 4 is by ZnO nano-rod array load C oS or CuS nano composite structure to electrode and TiO2/CdSe light anode institute
The current -voltage curve of assembled battery, as we can see from the figure open-circuit voltage of the ZnO/CuS to the battery of electrode assembling, short circuit
Electric current and fill factor respectively reach 0.55V, 14.01mA/cm2With 0.486, photoelectric conversion efficiency reaches 3.74%.ZnO/CoS
It is respectively 0.53V, 12.05mA/ to the open-circuit voltage of the battery of electrode assembling, short circuit current, fill factor and transfer efficiency
cm2, 0.482 and 2.89%.Fig. 5 is bent for current-voltage of the tradition Pt to electrode and the assembled battery of TiO2/CdSe light anode institute
Line, lower by cell photoelectric conversion performance of the Pt to electrode assembling as we can see from the figure, open-circuit voltage, is filled out short circuit current
It fills the factor and photoelectric conversion efficiency is respectively 0.55V, 8.87mA/cm2, 0.317 and 1.54%.Under identical experiment condition,
ZnO/CuS and ZnO/CoS is to the photoelectric conversion efficiency of the battery of electrode assembling respectively than traditional Pt to the battery of electrode assembling
Photoelectric conversion efficiency improves 141% and 86%.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (10)
1. being used for the nano-composite counter electrode of quantum dot sensitized solar battery, it is characterised in that: the nano-composite counter electrode
Including ZnO nano-rod array and in the composite nano metal sulfide particle of ZnO nano-rod array surface deposition.
2. the nano-composite counter electrode according to claim 1 for quantum dot sensitized solar battery, it is characterised in that:
The composite nano metal sulfide particle includes CoS nano particle.
3. the nano-composite counter electrode according to claim 1 for quantum dot sensitized solar battery, it is characterised in that:
The composite nano metal sulfide particle includes CuS nano particle.
4. the nano-composite counter electrode according to claim 1 for quantum dot sensitized solar battery, it is characterised in that:
The preparation method of the ZnO nano-rod array the following steps are included:
(1) preparation of ZnO seed layer
Be the precursor of ZnO with zinc acetate, using ethylene glycol monomethyl ether as solvent, using monoethanolamine as stabilizer, three mixing after
It is stirred to react at 60 DEG C 30 minutes, is then aged 24 hours at a constant temperature and forms uniform ZnO precursor colloidal sol, then revolved
It is applied to the electro-conductive glass substrate surface cleaned up, is put into Muffle furnace, is heat-treated 15 minutes at 200 DEG C with cured film,
Above-mentioned spin coating and heat treatment process 2~5 times are repeated, are finally putting into Muffle furnace, in 350 DEG C of annealing, 1 hour formation ZnO seed crystal
Layer；
(2) growth of ZnO nano-rod array
ZnO nano-rod array is prepared using cryochemistry bath sedimentation, growth solution is isometric zinc nitrate aqueous solution and hydrogen
The mixed liquor of aqueous solution of sodium oxide tiltedly suspends the ZnO seed layer substrate front surface prepared after mixed liquor stirs 1 hour downward
In growth solution, then the beaker for filling growth-promoting media is placed in thermostat water bath, is grown 30~60 minutes in 83 DEG C of water-baths
ZnO nano-rod array is formed, is rinsed well after taking-up with deionized water and ethyl alcohol, drying in 200 DEG C of Muffle furnace is placed in, it is standby
With.
5. the nano-composite counter electrode according to claim 4 for quantum dot sensitized solar battery, it is characterised in that:
The concentration of zinc acetate solution described in step (1) is 0.1~0.8mol/L, and the molar ratio of zinc acetate and monoethanolamine is 1:
1；
The concentration of zinc nitrate solution is 0.08mol/L in ZnO growth-promoting media described in step (2), and the concentration of sodium hydroxide solution is
1.8mol/L, the diameter of the ZnO nanorod of preparation are 80~150nm, and length is 1~3 μm.
6. the nano composite structure according to claim 4 for quantum dot sensitized solar battery is to electrode, feature
Be: electro-conductive glass substrate described in step (1) is FTO glass or ito glass, revolving speed when spin coating ZnO colloidal sol is 3000~
4000 revs/min, the time be 30 seconds.
7. the preparation method of the nano-composite counter electrode as claimed in claim 2 for quantum dot sensitized solar battery, special
Sign is: the ZnO nano-rod array prepared being immersed in cobalt acetate aqueous solution 1 minute, Co is made2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in sodium sulfide solution again 1 minute, makes Co2+With S2-React the CoS nano particle formed
It is adsorbed on the surface ZnO, is rinsed again with deionized water；Above procedure is a SILAR circulation.
8. the preparation method of the nano-composite counter electrode as claimed in claim 3 for quantum dot sensitized solar battery, special
Sign is: the ZnO nano-rod array prepared being immersed in acetic acid copper liquor 1 minute, Cu is made2+It is adsorbed on the surface ZnO, then
It is rinsed with deionized water；It is placed it in sodium sulfide solution again 1 minute, makes Cu2+With S2-React the CuS nano particle formed
It is adsorbed on the surface ZnO, is rinsed again with deionized water；Above procedure is a SILAR circulation.
9. the preparation method of the nano-composite counter electrode according to claim 7 for quantum dot sensitized solar battery,
It is characterized by:
The concentration of the cobalt acetate aqueous solution is 0.05~0.1mol/L, and deposition SILAR cycle-index is 3~12 times.
10. the preparation method of the nano-composite counter electrode according to claim 8 for quantum dot sensitized solar battery,
It is characterized by:
The concentration of the acetic acid copper liquor is 0.05~0.1mol/L, and deposition SILAR cycle-index is 3~12 times.
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| CN106328381A (en) * | 2016-11-23 | 2017-01-11 | 陕西理工学院 | All-solid-state quantum dot sensitized solar cell and preparation method thereof |
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| CN113403642B (en) * | 2021-05-24 | 2022-09-16 | 江苏大学 | BiVO 4 /Co 1-X Preparation method and application of S composite photoelectrode |
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