CN104036964B - The electrochemical preparation method of copper sulfide film - Google Patents
The electrochemical preparation method of copper sulfide film Download PDFInfo
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- CN104036964B CN104036964B CN201410280165.9A CN201410280165A CN104036964B CN 104036964 B CN104036964 B CN 104036964B CN 201410280165 A CN201410280165 A CN 201410280165A CN 104036964 B CN104036964 B CN 104036964B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention discloses the electrochemical preparation method of copper sulfide film, and the inorganic salts containing copper ion and the inorganic salts containing sodium are dissolved in dimethyl sulfoxide or dimethylformamide, then adds sulphur powder, and heating stirring dissolves sulphur powder, obtains electrolyte；Two electrode systems are used in the electrolyte, electro-deposition is carried out under the conditions of 70 90 DEG C, the copper sulfide film with specific structure is obtained on conductive substrates surface.This method step is simple, and cost is cheap, is easy to amplify, and the film that electrodeposition process can ensure to obtain has higher electric conductivity.The copper sulfide film can be used for dyestuff/quantum dot sensitized solar cell device directly as to electrode, have high electro catalytic activity and stability, while the adhesive force between the film and substrate is stronger, difficult for drop-off.
Description
Technical field
The present invention relates to solar cell field of batteries, and in particular to one kind is applied to dyestuff/quantum dot sensitized solar energy
Electrochemical preparation method of the high-performance copper sulfide film of battery to electrode.
Background technology
With expanding economy, the progress of society, people propose higher and higher requirement to the energy, among these solar energy
Due to rich reserves, safety, it is clean the advantages that obtain extensive concern.Obtaining electric power from solar energy needs to pass through solar-electricity
Pond carries out opto-electronic conversion to realize, has realized commercialized monocrystalline silicon, polysilicon, non-crystalline silicon and the semiconductive thin film sun at present
Energy battery still suffers from the shortcomings of preparation technology is complicated, expensive, it is difficult to large-scale application.
In order to solve the above problems, researcher has developed the cheap dye sensitization of solar electricity of a kind of new cost
Pond, its photoelectric transformation efficiency have reached more than 12%.The structure of DSSC is as shown in figure 1, mainly have
Light anode, electrolyte 4 and to the three parts of electrode 5 form.Under sunshine irradiation, the dye molecule 3 in light anode absorbs photon
Electron-hole pair is produced, the conduction band of wide bandgap semiconductor 2 wherein in electron injection light anode, hole is through the oxygen in electrolyte 4
Change-reduction electricity is compound with the electronics that is done work through external circuit under the electrocatalysis to electrode 5 to being transferred to electrode 5, completes
Whole electric cyclic process.
In recent years, researcher has developed quantum dot sensitized solar-electricity using semiconductor-quantum-point substitution dye molecule
Pond, its mechanism is similar to DSSC, but cost is low, extinction coefficient is high, band gap because quantum dot has in itself
The advantages that adjustable and more exciton effects and obtain extensive concern.
No matter in DSSC or quantum dot sensitized solar cell, to the performance of electrode to whole
The efficiency of battery device has important influence.At present, widely used in DSSC is metal to electrode
Platinum electrode, it is for the I in DSSC-/I3 -The electrocatalysis characteristic of oxidationreduction electricity pair is excellent, but golden
Belong to the expensive of platinum, influence the ratio of performance to price of whole battery；And widely used in quantum dot sensitized solar cell it is
S2-/Sn 2-Oxidationreduction electricity is right, and platinum electrode is relatively low to the electro catalytic activity of the electricity pair, widely used at present for transition gold
Belong to sulfide to electrode, but according to current research, this kind of sulfide electrode uses metal or alloy directly more and polysulfide
React to prepare, obtained electrode stability is poor, larger with practical application gap.Also have researcher be deposited in substrate or
It is allowed to react to obtain metal sulfide with polysulfide again after plating layer of metal to increase to electrode, stability, but still
It is difficult to the requirement for reaching practical application.
The content of the invention
It is an object of the invention to provide a kind of electrochemical deposition technique, to prepare, cost is cheap, electro catalytic activity is high and steady
Qualitative good copper sulfide film, to solve in dyestuff/quantum dot sensitized solar cell to the with high costs of electrode or stably
The problem of poor, the performance of this kind of solar cell is improved, pushes it against practical application.
The principle of the present invention is shown below：
Cu2++S(DMSO)+2e-→CuS↓
When copper ion and elemental sulfur be present simultaneously in the solution, in electro-reduction process, elemental sulfur is reduced to sulphur
Anion, while with solution copper ion react, electrode surface generate copper sulfide.
The preparation method of copper sulfide film provided by the invention comprises the following steps：
1) inorganic salts containing copper ion and the inorganic salts containing sodium ion are dissolved in dimethyl sulfoxide or dimethyl formyl
In amine, sulphur powder is then added, solution, which is heated up and stirred, dissolves sulphur powder, obtains electrolyte；
2) two electrode systems are used, electro-deposition are carried out under the conditions of 70-90 DEG C in electrolyte prepared by step 1), in conduction
Substrate surface obtains copper sulfide film.
Above-mentioned steps 1) configuration depositing copper sulphide film electrolyte.Wherein, the inorganic salts containing copper ion can be with
It is copper nitrate, copper sulphate etc.；The inorganic salts containing sodium ion can be sodium nitrate, sodium sulphate etc..Preferably, per 100mL
Solvent (dimethyl sulfoxide or dimethylformamide) dissolves 2~8mmol inorganic salts for containing copper ion and 2~8mmol contain sodium from
The inorganic salts of son, 1~5mmol sulphur powder is then added, solution is warming up to 60-90 DEG C, being stirred continuously is completely dissolved sulphur powder
Obtain electrolyte.In the specific embodiment of the present invention, weigh 3mmol copper nitrates and 3mmol sodium nitrate is dissolved in
Blue settled solution is formed in 60mL dimethyl sulfoxides, 1.8mmol sulphur powders are added into solution, solution are warming up to 80 DEG C, constantly
Stirring makes sulphur powder be completely dissolved to obtain electrolyte.
Above-mentioned steps 2) preferably, electro-deposition is carried out under 70-90 DEG C, 0.8~1.2 volt of voltage conditions, in conductive base
The copper sulfide film that bottom (such as FTO, ITO etc.) surface obtains has specific structure, as shown in Figures 2 and 3.
Copper sulfide film prepared by the inventive method can be used for dyestuff or quantum dot sensitized solar energy directly as to electrode
Battery device.
The copper sulfide film with specific structure, the party has been prepared by simple one-step electrochemistry deposition in the present invention
Method step is simple, and cost is cheap, is easy to amplify, and the film that electrodeposition process can ensure to obtain has higher electric conductivity, leads to
The copper sulfide film with specific micro-nano structure can also be obtained by crossing the optimization to electrodeposition condition, improve the ratio surface to electrode
The quantity of product and active site.Using copper sulfide film prepared by the inventive method as dyestuff/quantum dot solar electricity
Pond to electrode, there is high electro catalytic activity and stability, at the same the adhesive force of the film (elctro-catalyst) between substrate compared with
By force, it is difficult for drop-off.
Brief description of the drawings
Fig. 1 is the structure chart of dyestuff/quantum dot sensitized solar cell, wherein：1- electrically conducting transparent substrates；2- is attached to
Porous wide bandgap semiconductor in bright conductive substrates 1；3- adsorbs the dye molecule or quantum dot on the surface of wide bandgap semiconductor 2；
4- contains the electrolyte 4 of oxidationreduction electricity pair；5- have electro catalytic activity to electrode 5；Electrically conducting transparent substrate 1 with to electrode 5
It is connected with external circuit.
Fig. 2 is the scanning electron microscopic picture of copper sulfide film prepared by the embodiment of the present invention 1.
Fig. 3 is the powder x-ray diffraction figure of copper sulfide film prepared by the embodiment of the present invention 1, is indicated in figure with triangle
Diffraction maximum out comes from FTO substrates used by electro-deposition.
Fig. 4 is that the copper sulfide film that the embodiment of the present invention 1 is prepared is quantum dot sensitized solar cell to electrode
Current density voltage curve, by according to the solar cell that embodiment 2 assembles 100 milliwatts/square centimeter simulated solar
Measured under light irradiation.
Fig. 5 is that the copper sulfide film that the embodiment of the present invention 1 is prepared is quantum dot sensitized solar cell to electrode
Photoelectric transformation efficiency with irradiation time change, by according to the solar cell that embodiment 2 assembles 100 milliwatts/square li
Measured under the simulated solar light irradiation of rice.
Embodiment
Below in conjunction with the accompanying drawings, by embodiment, it is expanded on further technical scheme, but the protection model of the application
Enclose and do not limited by the actual conditions of these embodiments.
The electrochemical deposition of embodiment 1 prepares copper sulfide film
Step 1：Prepare the electrolyte of depositing copper sulphide film.Weigh 3 mMs of copper nitrates and 3 mMs of sodium nitrate dissolvings
Blue settled solution is formed in 60 milliliters of dimethyl sulfoxides (DMSO)；1.8 mMs of sulphur powder is added into the solution, by solution
80 DEG C are warming up to, being stirred continuously makes sulphur powder be completely dissolved to obtain electrolyte.
Step 2：Using two electrode systems, electro-deposition is carried out under the conditions of 80 DEG C, 0.8~1.2 volt of voltage is selected, is leading
Electric substrate surface electro-deposition obtains the copper sulfide film with specific structure.
The microscopic appearance of prepared copper sulfide film is as shown in Fig. 2 the structure of copper sulfide can be penetrated by the X- in Fig. 3
Ray diffraction diagram finds out that the film can be used for dyestuff or quantum dot sensitized solar cell device directly as to electrode.
The assembling quantum dot sensitization solar battery of embodiment 2
Step 1：Obtained on FTO surfaces by way of blade coating P25 that thickness is about 10 microns (titanium dioxide,
Degussa) porous membrane, using the mode of chemical bath deposition in one layer of cadmium selenide/cadmiumsulfide quantum dot of P25 superficial growths, every
Annealing can obtain the light anode of quantum dot sensitized solar cell under exhausted Oxygen Condition, and the light anode includes transparent in Fig. 1
Conductive substrates (FTO) 1, porous wide bandgap semiconductor film (P25 porous membranes) 2, and quantum dot 3；
Step 2：Prepare the electrolyte containing oxidation-reduction pair：The vulcanized sodium containing 1.0 mol/Ls and 1.0 is prepared to rub
You/liter elemental sulfur the aqueous solution, the electrolyte 4 as quantum dot solar cell；
Step 3：According to the method for preparing copper sulfide film described in embodiment 1 in FTO substrates electro-deposition copper sulfide, obtain
To for quantum dot solar cell to electrode 5；
Step 4：The light anode that respectively obtains steps 1 and 2,3 according to the structure shown in Fig. 1, electrolyte and to electrode assembling
Get up to obtain quantum dot sensitized solar cell device.
The open-circuit voltage of above-mentioned solar cell device is measured under 100 milliamps per square centimeter of simulated solar light irradiation
For 0.550 volt, short-circuit current density is 16.05 milliamps per square centimeter, fill factor, curve factor 48.9%, and photoelectric transformation efficiency is
4.36%, as shown in Figure 4.Under the conditions of prolonged exposure, the photoelectric transformation efficiency of the solar cell device slightly improves in the early stage
Gradually tend towards stability (4.18%) afterwards, illustrates good stability, as shown in Figure 5.
Claims (9)
1. a kind of preparation method of copper sulfide film, comprises the following steps：
1) inorganic salts containing copper ion and the inorganic salts containing sodium ion are dissolved in dimethyl sulfoxide or dimethylformamide,
Then sulphur powder is added, solution, which is heated up and stirred, dissolves sulphur powder, obtains electrolyte；
2) two electrode systems are used in electrolyte prepared by step 1), electro-deposition, voltage 0.8 is carried out under the conditions of 70-90 DEG C
~1.2 volts, copper sulfide film is obtained on conductive substrates surface.
2. preparation method according to claim 1, it is characterised in that the inorganic salts containing copper ion are described in step 1)
Copper nitrate or copper sulphate；The inorganic salts containing sodium ion are sodium nitrate or sodium sulphate.
3. preparation method according to claim 1, it is characterised in that step 1) is per 100mL dimethyl sulfoxides or dimethyl methyl
The inorganic salts that the inorganic salts and 2~8mmol that 2~8mmol of dissolving contains copper ion in acid amides contain sodium ion, add 1~5mmol
Sulphur powder.
4. preparation method according to claim 1, it is characterised in that be warming up to solution after adding sulphur powder in step 1)
60-90 DEG C, stirring is completely dissolved sulphur powder.
5. preparation method according to claim 1, it is characterised in that step 1) weighs 3mmol copper nitrates and 3mmol nitric acid
Sodium, which is dissolved in 60mL dimethyl sulfoxides, forms blue settled solution, and 1.8mmol sulphur powders are then added into solution, solution is heated up
To 80 DEG C, being stirred continuously makes sulphur powder be completely dissolved to obtain electrolyte.
6. preparation method according to claim 1, it is characterised in that step 2) is under conditions of electrolyte temperature is 80 DEG C
Carry out electro-deposition.
7. preparation method according to claim 1, it is characterised in that conductive substrates described in step 2) are FTO or ITO bases
Bottom.
8. copper sulfide film prepared by any preparation method of claim 1~7 is used as is used for the dye sensitization sun to electrode
The purposes of energy battery or quantum dot sensitized solar cell.
9. a kind of DSSC or quantum dot sensitized solar cell, including light anode, electrolyte and to electrode,
Characterized in that, described is the copper sulfide film prepared according to any preparation method of claim 1~7 to electrode.
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| CN104409218B (en) * | 2014-11-26 | 2018-02-16 | 东华大学 | A kind of Cu for quantum dot sensitized solar cellXS is to electrode and its preparation and application |
| CN105679544B (en) * | 2016-01-11 | 2018-03-13 | 上海交通大学 | A kind of DSSC copper manganese germanium sulphur is to electrode and preparation method thereof |
| CN109979645B (en) * | 2019-03-29 | 2020-11-10 | 合肥工业大学 | P-type copper sulfide transparent conductive film and preparation method thereof |
| CN111463432B (en) * | 2020-03-25 | 2021-06-15 | 陕西科技大学 | Graphene oxide composite three-dimensional copper sulfide battery cathode material with copper mesh in-situ growth, preparation method and application |
| CN111453759A (en) * | 2020-03-25 | 2020-07-28 | 陕西科技大学 | Copper foil in-situ growth three-dimensional copper sulfide negative electrode material for sodium ion battery, and preparation method and application thereof |
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Non-Patent Citations (6)
| Title |
|---|
| "Anodic Electrosynthesis of a Thin Film of Cu2S on a Gold Electrode. A Voltammetric，Nanoelectrogravimetric, and I/t Transient Study";Rodrigo del Rio等;《J. Phys. Chem. B》;20021114;第106卷;第12685页实验部分 * |
| "CuInS2:两步电沉积制备及性能";刘小雨等;《无机化学学报》;20081231;第24卷(第12期);第2035-2038页 * |
| "Electrochemical Growth of Cu-Zn Sulfides of Various Stoichiometries";M. Innocenti等;《Journal of The Electrochemical Society》;20131031;第161卷(第1期);第D14-D17页 * |
| "Incorporation of the TiO2 nanowire arrays photoanode and Cu2S nanorod arrays counter electrode on the photovoltaic performance of quantum dot sensitized solar cells";Zhuoyin Peng等;《Electrochimica Acta》;20140510;第135卷;摘要及实验部分2.4 * |
| "单晶CuS纳米线的电沉积合成及结构表征";王裕希等;《电子显微学报》;20140228;第33卷(第1期);第14页右栏1 硫化铜纳米线的制备 * |
| "硫化镉纳米薄膜的制备及其光电性能";陈海念等;《合成化学》;20121031;第20卷(第5期);第565页左栏实验部分1.2 * |
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