CN109326445B - Nano composite counter electrode for quantum dot sensitized solar cell and preparation method - Google Patents

Nano composite counter electrode for quantum dot sensitized solar cell and preparation method Download PDF

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CN109326445B
CN109326445B CN201811373717.5A CN201811373717A CN109326445B CN 109326445 B CN109326445 B CN 109326445B CN 201811373717 A CN201811373717 A CN 201811373717A CN 109326445 B CN109326445 B CN 109326445B
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counter electrode
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quantum dot
solar cell
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CN109326445A (en
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宋孝辉
马梓楠
田甜
闫勇
王立
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Henan Normal University
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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
    • 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
    • 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
    • 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
    • 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 invention discloses a nano composite counter electrode for a quantum dot sensitized solar cell and a preparation method thereof. The ZnO nano-rods in highly ordered arrangement have high conductivity, are favorable for rapidly transmitting electrons in an external circuit to CoS and CuS positions with high catalytic activity, and promote the electron transmission between a counter electrode and electrolyte. The composite nano-structure counter electrode is prepared by a full-solution method, has simple process, low cost and excellent performance, and can be used as a counter electrode of QDSSC (quantum dot-sensitized solar cell) under the same experimental conditions, and the photoelectric conversion efficiency of a cell assembled by ZnO/CuS and ZnO/CoS counter electrodes is respectively improved by 141% and 86% compared with that of a cell assembled by a traditional Pt counter electrode.

Description

Nano composite counter electrode for quantum dot sensitized solar cell and preparation method
Technical Field
The invention belongs to the field of solar energy utilization and nano materials, and particularly relates to a nano composite structure counter electrode for a quantum dot sensitized solar cell and a preparation method thereof.
Background
In the face of the gradual depletion of fossil energy and the serious environmental pollution caused by the use process of fossil energy, inexhaustible solar energy is an important countermeasure for solving the problem. Among various novel solar cells, Quantum Dot Sensitized Solar Cells (QDSSCs) which are simple in preparation process and low in cost have attracted extensive attention of researchers. Quantum dots have the unique advantages of tunable band structure, higher extinction coefficient, larger intrinsic dipole moment and multiple exciton regeneration effect, etc., compared to dye sensitizers (a. kongkannd, et al., j.am. chem.soc.,130(2008), 4007). Therefore, the research on QDSSC is very important to develop low-cost and high-efficiency solar cells.
The QDSSC mainly comprises a photoanode adsorbing quantum dots, an electrolyte and a counter electrode, wherein the counter electrode is used for transferring electrons of an external circuit toThe electrolyte is reduced and regenerated. In addition, the counter electrode can also accelerate the electron exchange rate between the redox couple in the electrolyte and the cathode, and plays a catalytic role. The Pt counter electrode commonly used in dye-sensitized cells not only has high cost, but also has S in polysulfide electrolyte2-The Pt is easy to adsorb on the surface of Pt, generates a poisoning effect, and reduces the catalytic performance of Pt on electrolyte (J.G.Radiich, et al., J.Phys.chem.Lett.,2(2011),2453), so that the filling factor of the battery is seriously influenced, which is also an important reason causing the low photoelectric conversion efficiency of the QDSSC, and therefore, Pt is not an optimal counter electrode material suitable for the QDSSC. In order to improve the electron transport rate of the counter electrode/electrolyte interface, various materials are tried to be used as the counter electrode in the 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., which overcome the problems of both cost and activity, but most of the existing counter electrode materials are obtained by corroding a metal foil, so that not only encapsulation is difficult, but also the electrolyte continuously corrodes the metal foil after the battery is formed, so that the stability of the battery is poor, and the practical purpose is difficult to achieve. The composite Nano-structure counter electrode combines the advantages of two Nano-materials, is the development trend of QDSSC counter electrode materials in the future, and reports about Nano-composite counter electrodes with high specific surface area and high conductivity, such as CuS-C (L.Li, et al., J.Phys.chem.C., 118(2014),16526) and ITO/CuS (Y.Jiang, et al., Nano Lett.,14(2014),365) core-shell arrays and the like, in the current article, and encouraging research results are obtained.
Disclosure of Invention
The invention aims to provide a nano composite material counter electrode prepared by a full-solution method, which combines a ZnO nanorod array with high conductivity and large specific surface area with a CoS and CuS catalyst with high catalytic activity, and forms a composite nano-structure counter electrode with high performance and low cost by exerting the synergistic advantages of the ZnO nanorod array and the CoS and CuS catalysts to solve the problems of high cost, low catalytic performance and poor stability of the conventional QDSSC counter electrode.
In order to achieve the purpose, the invention provides the following scheme:
the nano composite counter electrode for the quantum dot sensitized solar cell comprises a ZnO nanorod array and metal sulfide nano particles deposited on the surface of the ZnO nanorod array.
Preferably, the metal sulfide nanoparticles comprise CoS nanoparticles.
Preferably, the metal sulfide nanoparticles comprise CuS nanoparticles.
Preferably, the preparation method of the ZnO nanorod array comprises the following steps:
(1) preparation of ZnO seed crystal layer
Mixing zinc acetate as a ZnO precursor, ethylene glycol monomethyl ether as a solvent and monoethanolamine as a stabilizer, stirring and reacting for 30 minutes at 60 ℃, aging for 24 hours at a constant temperature to form uniform ZnO precursor sol, spin-coating the ZnO precursor sol on the surface of a cleaned conductive glass substrate, putting the conductive glass substrate into a muffle furnace, performing heat treatment for 15 minutes at 200 ℃ to solidify a film, repeating the spin-coating and heat treatment processes for 2-5 times, finally putting the conductive glass substrate into the muffle furnace, and annealing for 1 hour at 350 ℃ to form a ZnO seed crystal layer;
(2) growth of ZnO nanorod array
And preparing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method, wherein a growth solution is a mixed solution of a zinc nitrate aqueous solution and a sodium hydroxide aqueous solution which are equal in volume, the mixed solution is stirred for 1 hour, the front surface of the prepared ZnO seed crystal layer substrate is obliquely suspended in the growth solution downwards, then a beaker containing the growth solution is placed in a constant-temperature water bath kettle, the ZnO seed crystal layer substrate grows in water bath at 83 ℃ for 30-60 minutes to form the ZnO nanorod array, and the ZnO nanorod array is taken out, washed clean by deionized water and ethanol, and placed in a 200 ℃ muffle furnace for drying for later use.
Preferably, the concentration of the zinc acetate solution in the step (1) is 0.1-0.8 mol/L, and the molar ratio of the zinc acetate to the monoethanolamine is 1: 1; the concentration of a zinc nitrate solution in the ZnO growth solution in the step (2) is 0.08mol/L, the concentration of a sodium hydroxide solution is 1.8mol/L, and the prepared ZnO nanorod has the diameter of 80-150 nm and the length of 1-3 mu m.
Preferably, the conductive glass substrate is FTO glass or ITO glass, the rotating speed of the ZnO sol in the spin coating process is 3000-4000 r/min, and the time is 30 seconds.
The invention also provides a preparation method of the nano composite counter electrode for the quantum dot sensitized solar cell, which comprises the following steps:
depositing CoS nano particles on the surface of a ZnO nano rod by adopting a layer-by-layer ion adsorption and reaction method, and immersing the prepared ZnO nano rod array into a cobalt acetate aqueous solution for 1 minute to ensure that Co is dissolved in the aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; it was placed in an aqueous sodium sulfide solution for another 1 minute to allow Co to precipitate2+And S2-CoS nano particles formed by the reaction are adsorbed on the surface of ZnO and are washed by deionized water again; the above procedure is one SILAR cycle.
Preferably, the CuS nano-particles are deposited on the surfaces of the ZnO nano-rods by adopting a layer-by-layer ion adsorption and reaction method, and the prepared ZnO nano-rod array is immersed in the copper acetate aqueous solution for 1 minute to ensure that the Cu is dissolved in the copper acetate aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; it was then placed in an aqueous sodium sulfide solution for 1 minute to allow Cu to precipitate2+And S2-The CuS nano particles formed by the reaction are adsorbed on the surface of ZnO and are washed by deionized water again; the above procedure is one SILAR cycle.
Preferably, the concentration of the cobalt acetate/copper acetate aqueous solution is 0.05-0.1 mol/L, and the cycle number of SILAR deposition is 3-12.
The invention discloses the following technical effects:
compared with the existing counter electrode material, the composite nano-structure nanorod array counter electrode prepared by the invention has the following advantages:
(1) in the invention, ZnO plays a role in supporting a catalyst and transmitting electrons, and the ZnO nanorod array has a large specific surface area, can load more CoS and CuS catalysts, improves the contact area of the catalysts and electrolyte, and obviously reduces the transmission resistance of an electrolyte/counter electrode interface.
(2) The ZnO nano-rod with high ordered arrangement has high conductivity, and is favorable for quickly transmitting electrons in an external circuit to the ZnO nano-rod with high catalytic activityThe position of CoS and CuS promotes the electron transmission between the counter electrode and the electrolyte; meanwhile, because the gaps among the nanorod arrays are large, the electrolyte can smoothly permeate into the ZnO nanorods loaded with the metal sulfide catalyst, and S can be promoted2-/Sn2-A rapid reaction between the redox couple.
(3) The composite nano-structure counter electrode is prepared by a full-solution method, the process is simple, the cost is low, the performance is excellent, and the photoelectric conversion efficiency of a cell assembled by the ZnO/CuS counter electrode and the ZnO/CoS counter electrode is improved by 141% and 86% respectively compared with the photoelectric conversion efficiency of a cell assembled by the traditional Pt counter electrode under the same experimental conditions when the composite nano-structure counter electrode is used as the counter electrode of the QDSSC.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a ZnO nanorod array, wherein (a) is a cross-sectional SEM image, and (b) is a surface SEM image;
FIG. 2 is a scanning electron microscope picture of a CoS catalyst-supported nanocomposite structure counter electrode of the ZnO nanorod array prepared in example 1;
FIG. 3 is a scanning electron microscope picture of a nanocomposite structure counter electrode of the ZnO nanorod array loaded CuS catalyst prepared in example 2;
figure 4 is a graph of current-voltage curves for QDSSC versus electrode assembly for the nanocomposite structures prepared in examples 1-2.
FIG. 5 is a comparative example of a conventional Pt counter electrode and TiO2Current-voltage curve of cell assembled with CdSe photoanode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
Preparing ZnO nanorod array loaded CoS catalyst nano composite structure counter electrode
(1) Preparing a ZnO seed crystal layer: dissolving zinc acetate into ethylene glycol monomethyl ether as a solvent to prepare a solution with the concentration of 0.3mol/L, then dropwise adding monoethanolamine with the same molar concentration into the solution as a stabilizer, heating and stirring the prepared mixed solution in a water bath at 60 ℃ for 30 minutes, and finally aging in a thermostat at 30 ℃ for 24 hours to obtain the sol spin-coating solution. And then spin-coating the sol on cleaned FTO glass by adopting a process of rotating at 3000 r/min for 30 seconds, and putting the cleaned FTO glass into a 200 ℃ muffle furnace for annealing for 15 minutes to solidify the film. After the spin coating and annealing processes are repeated twice, the mixture is put into a muffle furnace and gradually heated to 350 ℃ at the speed of 5 ℃/min, and is annealed for 30 minutes at the temperature, and the sol is completely decomposed and crystallized to form the ZnO seed crystal layer film.
(2) Growing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method: firstly, respectively preparing 50ml of 0.08mol/L zinc nitrate aqueous solution and 50ml of 1.8mol/L sodium hydroxide aqueous solution, uniformly stirring, slowly adding the zinc nitrate aqueous solution into the sodium hydroxide aqueous solution, stirring the mixed solution for 1 hour, suspending the front surface of a ZnO seed crystal layer substrate prepared in advance in the growth solution in an inclined mode, growing for 30 minutes in a constant-temperature water bath kettle at 80 ℃, taking out a grown nanorod array film after the reaction is finished, respectively washing the nanorod array film with deionized water and ethanol, and drying the nanorod array film in a 200 ℃ muffle furnace for later use.
(3) Depositing CoS catalytic material nano on the surface of ZnO nano-rod by adopting a layer-by-layer ion adsorption and reaction methodRice particles: soaking the prepared ZnO nanorod array into 0.1mol/L cobalt acetate aqueous solution for 1 minute to ensure that Co is dissolved in the aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; then placed in 0.1mol/L sodium sulfide aqueous solution for 1 minute, Co2+And S2-The reaction forms CoS nano particles which are adsorbed on the surface of ZnO, and the CoS nano particles are washed by deionized water again. The above process is a SILAR cycle, and the cycle is repeated for 9 times to prepare the ZnO nanorod array loaded CoS counter electrode.
(II) preparation of CdSe quantum dot sensitized porous TiO2Photoanode (TiO)2/CdSe)
Dyesol-18NRT TiO by Screen printing2Coating the slurry on FTO conductive glass, annealing in a muffle furnace at 500 deg.C for 30 min, cooling to room temperature to form a film with a thickness of 10 μm and an area of 5 × 5mm2Porous TiO of (2)2And an electrode. Then depositing CdSe quantum dots on the surface of the porous TiO2 by an electrochemical deposition method (X.Song, et al., Electrochimica Acta,2013,108,449) to form TiO2a/CdSe electrode.
(III) assembling and testing the quantum dot sensitized solar cell
The prepared TiO is mixed with2The CdSe photo-anode is arranged on the table top, a cut heat-sealing film frame (50 mu m) is stacked on the periphery of the electrode, then a ZnO nanorod array load CoS nano composite structure counter electrode is covered on the surface of the heat-sealing film, and polysulfide electrolyte (1mol/L Na) is filled into a small hole punched in advance on the counter electrode after the counter electrode is heated and packaged by a heat sealing machine2S and 1mol/LS powder aqueous solution), and then sealing the small holes to complete the preparation of the quantum dot sensitized solar cell. The assembled battery is 100mW/cm2(AM 1.5) current-voltage curves were tested under simulated sunlight.
Example 2
Preparing ZnO nanorod array loaded CuS catalyst nano composite structure counter electrode
(1) Preparing a ZnO seed crystal layer: the same as in example 1.
(2) Growing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method: the same as in example 1.
(3) By a layer-by-layer ion adsorption and reaction method in ZDepositing CuS catalytic material nanoparticles on the surface of the nO nanorod: immersing the prepared ZnO nano-rod array into 0.1mol/L copper acetate water solution for 1 minute to ensure that Cu2+Adsorbing on the surface of ZnO, and then washing with deionized water; then placed in 0.1mol/L sodium sulfide aqueous solution for 1 minute, Cu2+And S2-And (4) absorbing the CuS nano particles formed by the reaction on the surface of ZnO, and washing with deionized water again. The above process is a SILAR cycle, and the cycle is repeated for 10 times to prepare the ZnO nanorod array loaded CuS counter electrode.
(II) preparation of CdSe quantum dot sensitized porous TiO2Photoanode (TiO)2/CdSe)
Dyesol-18NRT TiO by Screen printing2Coating the slurry on FTO conductive glass, annealing in a muffle furnace at 500 deg.C for 30 min, cooling to room temperature to form a film with a thickness of 10 μm and an area of 5 × 5mm2Porous TiO of (2)2And an electrode. Then depositing CdSe quantum dots on the surface of the porous TiO2 by an electrochemical deposition method (X.Song, et al., Electrochimica Acta,2013,108,449) to form TiO2a/CdSe electrode.
(III) assembling and testing the quantum dot sensitized solar cell
The prepared TiO is mixed with2The CdSe photo-anode is arranged on the table top, a cut heat-sealing film frame (50 mu m) is stacked around the electrode, then a ZnO nanorod array loaded CuS nano-composite structure counter electrode is covered on the surface of the heat-sealing film, and polysulfide electrolyte (1mol/L Na) is filled into a small hole punched in advance on the counter electrode after the counter electrode is heated and packaged by a heat sealing machine2S and 1mol/LS powder aqueous solution), and then sealing the small holes to complete the preparation of the quantum dot sensitized solar cell. The assembled battery is 100mW/cm2(AM 1.5) current-voltage curves were tested under simulated sunlight.
Example 3
Preparing ZnO nanorod array loaded CoS catalyst nano composite structure counter electrode
(1) Preparing a ZnO seed crystal layer: dissolving zinc acetate into ethylene glycol monomethyl ether as a solvent to prepare a solution with the concentration of 0.8mol/L, then dropwise adding monoethanolamine with the same molar concentration into the solution as a stabilizer, heating and stirring the prepared mixed solution in a water bath at 60 ℃ for 30 minutes, and finally aging in a thermostat at 30 ℃ for 24 hours to obtain the sol spin-coating solution. And spin-coating the sol on the cleaned ITO glass by adopting a process with the rotating speed of 4000 revolutions per minute and the time of 30 seconds, and putting the cleaned ITO glass into a 200-DEG C muffle furnace for annealing for 15 minutes to solidify the film. After the spin coating and annealing processes are repeated twice, the mixture is put into a muffle furnace and gradually heated to 350 ℃ at the speed of 5 ℃/min, and is annealed for 30 minutes at the temperature, and the sol is completely decomposed and crystallized to form the ZnO seed crystal layer film.
(2) Growing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method: the same as in example 1.
(3) Depositing CoS catalytic material nanoparticles on the surface of the ZnO nanorod by adopting a layer-by-layer ion adsorption and reaction method: soaking the prepared ZnO nanorod array into 0.05mol/L copper acetate aqueous solution for 1 minute to ensure that Co is dissolved in the aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; then placed in 0.1mol/L sodium sulfide aqueous solution for 1 minute, Cu2+And S2-And (4) absorbing the CuS nano particles formed by the reaction on the surface of ZnO, and washing with deionized water again. The above process is a SILAR cycle, and the cycle is repeated for 12 times to prepare the ZnO nanorod array loaded CoS counter electrode.
(II) preparation of CdSe quantum dot sensitized porous TiO2Photoanode (TiO)2/CdSe)
Dyesol-18NRT TiO by Screen printing2Coating the slurry on ITO conductive glass, annealing in a muffle furnace at 500 deg.C for 30 min, cooling to room temperature to form a film with a thickness of 10 μm and an area of 5 × 5mm2Porous TiO of (2)2And an electrode. Then depositing CdSe quantum dots on the surface of the porous TiO2 by an electrochemical deposition method (X.Song, et al., Electrochimica Acta,2013,108,449) to form TiO2a/CdSe electrode.
(III) assembling and testing the quantum dot sensitized solar cell
The prepared TiO is mixed with2the/CdSe photo-anode is arranged on the table top, the cut heat-sealing film frame (50 mu m) is overlapped around the electrode, and then the surface of the heat-sealing film is covered with a ZnO nano-rod array loaded CoS nano compositeThe structure of counter electrode is heated and sealed by a heat sealing machine, and then polysulfide electrolyte (1mol/L Na) is filled into the counter electrode through a small hole which is punched in advance2S and 1mol/LS powder aqueous solution), and then sealing the small holes to complete the preparation of the quantum dot sensitized solar cell.
Example 4
Preparing ZnO nanorod array loaded CuS catalyst nano composite structure counter electrode
(1) Preparing a ZnO seed crystal layer: the same as in example 3.
(2) Growing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method: the same as in example 1.
(3) Depositing CuS catalytic material nano particles on the surface of the ZnO nano rod by adopting a layer-by-layer ion adsorption and reaction method: immersing the prepared ZnO nano-rod array into 0.1mol/L copper acetate water solution for 1 minute to ensure that Cu2+Adsorbing on the surface of ZnO, and then washing with deionized water; then placed in 0.1mol/L sodium sulfide aqueous solution for 1 minute, Cu2+And S2-And (4) absorbing the CuS nano particles formed by the reaction on the surface of ZnO, and washing with deionized water again. The above process is a SILAR cycle, and the cycle is repeated for 8 times to prepare the ZnO nanorod array loaded CuS counter electrode.
(II) preparation of CdSe quantum dot sensitized porous TiO2Photoanode (TiO)2/CdSe)
Dyesol-18NRT TiO by Screen printing2Coating the slurry on ITO conductive glass, annealing in a muffle furnace at 500 deg.C for 30 min, cooling to room temperature to form a film with a thickness of 10 μm and an area of 5 × 5mm2Porous TiO of (2)2And an electrode. Then depositing CdSe quantum dots on the surface of the porous TiO2 by an electrochemical deposition method (X.Song, et al., Electrochimica Acta,2013,108,449) to form TiO2a/CdSe electrode.
(III) assembling and testing the quantum dot sensitized solar cell
The prepared TiO is mixed with2Placing the CdSe photo-anode on the table top, stacking the cut heat-sealing film frame (50 μm) around the electrode, covering the heat-sealing film with a ZnO nanorod array loaded CuS nano-composite structure counter electrode, heating and packaging with a heat-sealing machine, and passing through the counter electrodeA hole pre-punched on the electrode is filled with polysulfide electrolyte (1mol/L Na)2S and 1mol/LS powder aqueous solution), and then sealing the small holes to complete the preparation of the quantum dot sensitized solar cell.
Comparative example
Preparation of CdSe quantum dot sensitized porous TiO2Photoanode (TiO)2/CdSe)
Dyesol-18NRTTiO by Screen printing2Coating the slurry on ITO conductive glass, annealing in a muffle furnace at 500 deg.C for 30 min, cooling to room temperature to form a film with a thickness of 10 μm and an area of 5 × 5mm2Porous TiO of (2)2And an electrode. Then depositing CdSe quantum dots on the surface of the porous TiO2 by an electrochemical deposition method (X.Song, et al., Electrochimica Acta,2013,108,449) to form TiO2a/CdSe electrode.
(II) assembling and testing the quantum dot sensitized solar cell
The prepared TiO is mixed with2The CdSe photo-anode is placed on the table top, and the cut heat-sealing film frame (50 μm) is stacked around the electrode, then the conventional Pt counter electrode is covered on the surface of the heat-sealing film, and after the heat-sealing film is heated and sealed by a heat sealing machine, polysulfide electrolyte (1mol/L Na) is filled into the pre-punched small hole on the counter electrode2S and 1mol/L S powder aqueous solution), and then sealing the small holes to complete the preparation of the quantum dot sensitized solar cell. The assembled battery is 100mW/cm2(AM 1.5) current-voltage curves were tested under simulated sunlight.
FIG. 1(a) is a sectional SEM image of a ZnO nanorod array, from which it can be seen that nanorods grow directionally perpendicular to the FTO substrate, are highly uniform in orientation, are in the form of an array, and have discrete order from rod to rod. The length of the nanorods is about 2 μm. FIG. 1(b) is a SEM image of the surface of the ZnO nanorod array, from which it can be seen that the nanorods are closely and uniformly arranged and have a uniform diameter distribution of about 50 nm.
FIG. 2 is a surface SEM image of a CoS catalyst nano composite structure loaded on a ZnO nano array as a counter electrode, and some CoS nano particles are deposited on the surface of ZnO nano rods, so that the structure improves the contact area of the counter electrode and electrolyte, and is helpful for improving the catalytic activity of the counter electrode.
FIG. 3 is a surface SEM image of a ZnO nano array loaded CuS catalyst nano composite structure counter electrode, and a plurality of CuS nano particles are deposited on the surface of a ZnO nano rod, so that the contact area of the counter electrode and electrolyte is increased by the structure, and the catalytic activity of the counter electrode is improved.
FIG. 4 is the current-voltage curve of the cell assembled by the CoS or CuS nano composite structure loaded by the ZnO nano rod array and the TiO2/CdSe photo-anode, and it can be seen from the graph that the open-circuit voltage, the short-circuit current and the filling factor of the cell assembled by the ZnO/CuS counter electrode respectively reach 0.55V and 14.01mA/cm2And 0.486, the photoelectric conversion efficiency reached 3.74%. The open-circuit voltage, short-circuit current, fill factor and conversion efficiency of the ZnO/CoS counter electrode assembled battery are respectively 0.53V and 12.05mA/cm20.482 and 2.89%. FIG. 5 is a current-voltage curve of a cell assembled by a conventional Pt counter electrode and a TiO2/CdSe photo-anode, and it can be seen from the graph that the cell assembled by the Pt counter electrode has low photoelectric conversion performance, and the open-circuit voltage, the short-circuit current, the fill factor and the photoelectric conversion efficiency are respectively 0.55V and 8.87mA/cm20.317 and 1.54%. Under the same experimental conditions, the photoelectric conversion efficiency of the ZnO/CuS and ZnO/CoS counter electrode assembled batteries is respectively improved by 141% and 86% compared with that of the conventional Pt counter electrode assembled batteries.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (8)

1. A nano-composite counter electrode for a quantum dot sensitized solar cell, characterized in that: the nano composite counter electrode comprises a ZnO nanorod array and metal sulfide nano particles deposited on the surface of the ZnO nanorod array;
the metal sulfide nanoparticles include CoS nanoparticles and CuS nanoparticles.
2. The nanocomposite counter electrode for a quantum dot sensitized solar cell according to claim 1, characterized in that: the preparation method of the ZnO nanorod array comprises the following steps:
(1) preparation of ZnO seed crystal layer
Mixing zinc acetate as a ZnO precursor, ethylene glycol monomethyl ether as a solvent and monoethanolamine as a stabilizer, stirring and reacting for 30 minutes at 60 ℃, aging for 24 hours at a constant temperature to form uniform ZnO precursor sol, spin-coating the ZnO precursor sol on the surface of a cleaned conductive glass substrate, putting the conductive glass substrate into a muffle furnace, performing heat treatment for 15 minutes at 200 ℃ to solidify a film, repeating the spin-coating and heat treatment processes for 2-5 times, finally putting the conductive glass substrate into the muffle furnace, and annealing for 1 hour at 350 ℃ to form a ZnO seed crystal layer;
(2) and preparing the ZnO nanorod array by adopting a low-temperature chemical bath deposition method for growth of the ZnO nanorod array, wherein a growth solution is a mixed solution of a zinc nitrate aqueous solution and a sodium hydroxide aqueous solution which are equal in volume, the mixed solution is stirred for 1 hour, the front surface of the prepared ZnO seed crystal layer substrate is obliquely suspended in the growth solution downwards, then a beaker containing the growth solution is placed in a constant-temperature water bath kettle, the ZnO nanorod array is formed after the ZnO seed crystal layer substrate grows in water bath at 83 ℃ for 30-60 minutes, and the ZnO nanorod array is washed clean by deionized water and ethanol after being taken out and is placed in a muffle furnace at 200 ℃ for drying for later use.
3. The nanocomposite counter electrode for a quantum dot sensitized solar cell according to claim 2, characterized in that: the concentration of the zinc acetate solution in the step (1) is 0.1-0.8 mol/L, and the molar ratio of zinc acetate to monoethanolamine is 1: 1;
the concentration of the zinc nitrate solution in the growth solution in the step (2) is 0.08mol/L, the concentration of the sodium hydroxide solution is 1.8mol/L, and the prepared ZnO nanorod has the diameter of 80-150 nm and the length of 1-3 mu m.
4. The nanocomposite structure counter electrode for a quantum dot sensitized solar cell according to claim 2, characterized in that: the conductive glass substrate in the step (1) is FTO glass or ITO glass, the rotating speed of the ZnO sol in the spin coating process is 3000-4000 r/min, and the time is 30 seconds.
5. The method of preparing a nanocomposite counter electrode for a quantum dot sensitized solar cell according to claim 1, wherein: soaking the prepared ZnO nanorod array into cobalt acetate aqueous solution for 1 minute to ensure that Co is dissolved in the aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; it was placed in an aqueous sodium sulfide solution for another 1 minute to allow Co to precipitate2+And S2-CoS nano particles formed by the reaction are adsorbed on the surface of ZnO and are washed by deionized water again; the above procedure is one SILAR cycle.
6. The method of preparing a nanocomposite counter electrode for a quantum dot sensitized solar cell according to claim 1, wherein: immersing the prepared ZnO nanorod array into a copper acetate aqueous solution for 1 minute to ensure that Cu is dissolved in the aqueous solution2+Adsorbing on the surface of ZnO, and then washing with deionized water; it was then placed in an aqueous sodium sulfide solution for 1 minute to allow Cu to precipitate2+And S2-The CuS nano particles formed by the reaction are adsorbed on the surface of ZnO and are washed by deionized water again; the above procedure is one SILAR cycle.
7. The method of claim 5, wherein the method comprises the steps of: the concentration of the cobalt acetate aqueous solution is 0.05-0.1 mol/L, and the cycle number of SILAR deposition is 3-12.
8. The method of claim 6, wherein the method comprises the steps of: the concentration of the copper acetate aqueous solution is 0.05-0.1 mol/L, and the cycle number of SILAR deposition is 3-12.
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