CN104036964A - Electrochemical preparation method for copper sulphide films - Google Patents
Electrochemical preparation method for copper sulphide films Download PDFInfo
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- CN104036964A CN104036964A CN201410280165.9A CN201410280165A CN104036964A CN 104036964 A CN104036964 A CN 104036964A CN 201410280165 A CN201410280165 A CN 201410280165A CN 104036964 A CN104036964 A CN 104036964A
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses an electrochemical preparation method for copper sulphide films. The electrochemical preparation method for the copper sulphide films comprises the following steps of dissolving inorganic salt containing cupric ions and inorganic salt containing sodium into dimethylsulfoxide or dimethylformamide; adding powdered sulfur in the mixture; heating and stirring the mixture until the powdered sulfur is dissolved so as to obtain electrolyte; performing electrolytic deposition on the electrolyte at the temperature of 70-90 DEG C by using two electrode systems so as to obtain the copper sulphide films with the specific structures on the surface of a conductive substrate. The steps of the method are simple; the cost is low; the copper sulphide films are enlarged easily; and the obtained films have high conductivity in an electrolytic deposition process. The copper sulphide films can directly serve as solar batteries for performing sensitization on dye/quantum dots of the electrodes; the electrocatalytic activity and the stability are high; and the films can be adhered to a substrate firmly and cannot be separated from the substrate easily.
Description
Technical field
The present invention relates to solar cell field of batteries, be specifically related to the electrochemical preparation method of a kind of high-performance copper sulfide film that is applied to dyestuff/quantum dot sensitized solar cell to electrode.
Background technology
Along with the progress of expanding economy, society, people have proposed more and more higher requirement to the energy, this wherein solar energy because the advantages such as reserves are abundant, safe, clean have obtained concern widely.Obtaining electric power from solar energy need to carry out opto-electronic conversion by solar cell and realize, realize at present business-like monocrystalline silicon, polysilicon, amorphous silicon and semiconductor thin-film solar cell and still had complicated process of preparation, the shortcoming such as expensive, be difficult to large-scale application.
In order to address the above problem, researcher has developed the novel DSSC with low cost of a class, and its photoelectric conversion efficiency has reached more than 12%.The structure of DSSC as shown in Figure 1, mainly contains light anode, electrolyte 4 and electrode 5 three parts is formed.Under solar light irradiation, dye molecule 3 in light anode absorbs photon and produces electron-hole pair, the wherein conduction band of wide bandgap semiconductor 2 in electron beam light inlet anode, oxidation-reduction the electricity of hole in electrolyte 4 is to being transferred to electrode 5, with electron recombination through external circuit acting, complete whole electric cyclic process under to the electrocatalysis of electrode 5.
In recent years, researcher uses semiconductor-quantum-point to replace dye molecule and has developed quantum dot sensitized solar cell, its mechanism is similar to DSSC, but because quantum dot itself has that cost is low, extinction coefficient is high, band gap is adjustable and the advantage such as many exciton effects has obtained extensive concern.
No matter, in DSSC or quantum dot sensitized solar cell, the performance of electrode is had to important impact to the efficiency of whole battery device.At present, widely used in DSSC is metal platinum electrode to electrode, and it is for the I in DSSC
-/ I
3 -the right electrocatalysis characteristic of oxidation-reduction electricity is good, but metal platinum is expensive, affects the ratio of performance to price of whole battery; And widely used in quantum dot sensitized solar cell be S
2-/ S
n 2-oxidation-reduction electricity is right, platinum electrode is lower to the right electro catalytic activity of this electricity, at present widely used is that transient metal sulfide is to electrode, but according to current research, this class sulfide electrode adopts metal or alloy directly to react to prepare with polysulfide more, the electrode stability making is poor, larger with practical application gap.Also have researcher's evaporation or electroplate after layer of metal and make it to react and obtain metal sulfide to electrode with polysulfide again in substrate, stability increases, but is still difficult to reach the requirement of practical application.
Summary of the invention
The object of this invention is to provide that a kind of electrochemical deposition technique is cheap in order to preparation cost, electro catalytic activity is high and the copper sulfide film of good stability, in order to solve the problem of the with high costs or stable difference to electrode in dyestuff/quantum dot sensitized solar cell, the performance that improves this class solar cell, pushes it against practical application.
Principle of the present invention is shown below:
Cu
2++S(DMSO)+2e
-→CuS↓
There is copper ion and elemental sulfur in solution time, in electro-reduction process, elemental sulfur is reduced to the anion of sulphur simultaneously, reacts with the copper ion in solution simultaneously, generates copper sulfide at electrode surface.
The preparation method of copper sulfide film provided by the invention comprises the following steps:
1) inorganic salts that contain copper ion and the inorganic salts that contain sodium ion are dissolved in methyl-sulfoxide or dimethyl formamide, then add sulphur powder, solution being heated up and stir dissolves sulphur powder, obtains electrolyte;
2) use two electrode systems, in step 1) under 70-90 DEG C of condition, carry out electro-deposition in the electrolyte prepared, obtain copper sulfide film on conductive substrates surface.
Above-mentioned steps 1) electrolyte of configuration depositing copper sulphide film.Wherein, the inorganic salts that contain copper ion described in can be copper nitrate, copper sulphate etc.; The described inorganic salts that contain sodium ion can be sodium nitrate, sodium sulphate etc.Preferably, the inorganic salts that the inorganic salts that every 100mL solvent (methyl-sulfoxide or dimethyl formamide) dissolving 2～8mmol contains copper ion and 2～8mmol contain sodium ion, then add the sulphur powder of 1～5mmol, solution is warming up to 60-90 DEG C, and constantly stirring is dissolved sulphur powder completely and is obtained electrolyte.In a specific embodiment of the present invention, taking 3mmol copper nitrate and 3mmol sodium nitrate is dissolved in and in 60mL methyl-sulfoxide, forms blue settled solution, in solution, add 1.8mmol sulphur powder, solution is warming up to 80 DEG C, constantly stirring is dissolved sulphur powder completely and is obtained electrolyte.
Above-mentioned steps 2) preferred, at 70-90 DEG C, under the voltage conditions of 0.8～1.2 volt, carry out electro-deposition, the copper sulfide film such as, obtaining on conductive substrates (FTO, ITO etc.) surface has specific structure, as shown in Figures 2 and 3.
Copper sulfide film prepared by the inventive method can be directly as to electrode for dyestuff or quantum dot sensitized solar cell device.
The present invention has prepared the copper sulfide film with ad hoc structure by a simple one-step electrochemistry deposition, the method step is simple, with low cost, be easy to amplify, electrodeposition process can ensure that the film obtaining has higher conductivity, by can also obtain having the copper sulfide film of specific micro-nano structure to the optimization of electrodeposition condition, improve specific area to electrode and the quantity of active site.Use the copper sulfide film prepared of the inventive method as dyestuff/quantum dot solar cell to electrode, there is high electro catalytic activity and stability, the adhesive force between this film (eelctro-catalyst) and substrate is stronger simultaneously, difficult drop-off.
Brief description of the drawings
Fig. 1 is the structure chart of dyestuff/quantum dot sensitized solar cell, wherein: the substrate of 1-electrically conducting transparent; 2-is attached to the porous wide bandgap semiconductor in electrically conducting transparent substrate 1; 3-is adsorbed on dye molecule or the quantum dot on wide bandgap semiconductor 2 surfaces; 4-contains the right electrolyte 4 of oxidation-reduction electricity; 5-have electro catalytic activity to electrode 5; Electrically conducting transparent substrate 1 with electrode 5 is connected with external circuit.
Fig. 2 is the ESEM picture of the copper sulfide film prepared of the embodiment of the present invention 1.
Fig. 3 is the powder x-ray diffraction figure of the copper sulfide film prepared of the embodiment of the present invention 1, the FTO substrate that the diffraction maximum marking with triangle in figure adopts from electro-deposition.
Fig. 4 is that the copper sulfide film that the embodiment of the present invention 1 prepares is the current density voltage curve of the quantum dot sensitized solar cell to electrode, is recorded under the simulated solar irradiation of 100 milliwatt/square centimeters by the solar cell of assembling according to embodiment 2.
Fig. 5 be copper sulfide film that the embodiment of the present invention 1 prepares be the photoelectric conversion efficiency of the quantum dot sensitized solar cell to electrode with the variation of irradiation time, recorded under the simulated solar irradiation of 100 milliwatt/square centimeters by the solar cell of assembling according to embodiment 2.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, further set forth technical scheme of the present invention, but the application's protection range is not subject to the restriction of the actual conditions of these embodiment.
Embodiment 1 electrochemical deposition is prepared copper sulfide film
Step 1: the electrolyte of preparation depositing copper sulphide film.Take 3 mMs of copper nitrates and 3 mMs of sodium nitrate and be dissolved in the blue settled solution of formation in 60 milliliters of methyl-sulfoxides (DMSO); To the sulphur powder that adds 1.8 mMs in this solution, solution is warming up to 80 DEG C, constantly stir and sulphur powder is dissolved completely obtain electrolyte.
Step 2: use two electrode systems, carry out electro-deposition under 80 DEG C of conditions, select the voltage of 0.8～1.2 volt, obtain having the copper sulfide film of ad hoc structure in conductive substrates surface electrical deposition.
The microscopic appearance of prepared copper sulfide film as shown in Figure 2, can find out by the x-ray diffraction pattern in Fig. 3 by the structure of copper sulfide, this film can be directly as to electrode for dyestuff or quantum dot sensitized solar cell device.
Embodiment 2 assembling quantum dot sensitization solar batteries
Step 1: obtain by the mode of blade coating the P25 (titanium dioxide that thickness is about 10 microns on FTO surface, Degussa) porous membrane, utilize the mode of chemical bath deposition at P25 superficial growth one deck cadmium selenide/cadmiumsulfide quantum dot, under starvation condition, annealing can obtain the light anode of quantum dot sensitized solar cell, this light anode comprises the electrically conducting transparent substrate (FTO) 1 in Fig. 1, porous wide bandgap semiconductor film (P25 porous membrane) 2, and quantum dot 3;
Step 2: the electrolyte that preparation contains oxidation-reduction pair: the aqueous solution of the vulcanized sodium that preparation contains 1.0 mol/L and the elemental sulfur of 1.0 mol/L, as the electrolyte 4 of quantum dot solar cell;
Step 3: according to the method for preparing copper sulfide film described in embodiment 1 at FTO substrate substrates copper sulfide, obtain for quantum dot solar cell to electrode 5;
Step 4: light anode, electrolyte step 1,2,3 being obtained respectively according to the structure shown in Fig. 1 and electrode assembling is got up to obtain quantum dot sensitized solar cell device.
The open circuit voltage that records above-mentioned solar cell device under the simulated solar irradiation of 100 milliamperes/square centimeter is 0.550 volt, and short-circuit current density is 16.05 milliamperes/square centimeter, fill factor, curve factor 48.9%, and photoelectric conversion efficiency is 4.36%, as shown in Figure 4.Under prolonged exposure condition, after the photoelectric conversion efficiency of this solar cell device is slightly improved in the early stage, tend towards stability gradually (4.18%), shown good stability, as shown in Figure 5.
Claims (10)
1. a preparation method for copper sulfide film, comprises the following steps:
1) inorganic salts that contain copper ion and the inorganic salts that contain sodium ion are dissolved in methyl-sulfoxide or dimethyl formamide, then add sulphur powder, solution being heated up and stir dissolves sulphur powder, obtains electrolyte;
2) in step 1) use two electrode systems in the electrolyte prepared, under 70-90 DEG C of condition, carry out electro-deposition, obtain copper sulfide film on conductive substrates surface.
2. preparation method according to claim 1, is characterized in that step 1) described in contain copper ion inorganic salts be copper nitrate or copper sulphate; The described inorganic salts that contain sodium ion are sodium nitrate or sodium sulphate.
3. preparation method according to claim 1, is characterized in that step 1) dissolve the inorganic salts that inorganic salts that 2～8mmol contains copper ion and 2～8mmol contain sodium ion in every 100mL methyl-sulfoxide or dimethyl formamide, add 1～5mmol sulphur powder.
4. preparation method according to claim 1, is characterized in that step 1) in solution is warming up to 60-90 DEG C after adding sulphur powder, stir sulphur powder dissolved completely.
5. preparation method according to claim 1, it is characterized in that, step 1) take 3mmol copper nitrate and 3mmol sodium nitrate and be dissolved in and in 60mL methyl-sulfoxide, form blue settled solution, then in solution, add 1.8mmol sulphur powder, solution is warming up to 80 DEG C, and constantly stirring is dissolved sulphur powder completely and is obtained electrolyte.
6. preparation method according to claim 1, is characterized in that step 2) voltage of electro-deposition is 0.8～1.2 volt.
7. preparation method claimed in claim 1, is characterized in that step 2) be to carry out electro-deposition under the condition of 80 DEG C at electrolyte temperature.
8. preparation method according to claim 1, is characterized in that step 2) described in conductive substrates be FTO or ITO substrate.
9. the copper sulfide film that prepared by the arbitrary described preparation method of claim 1～8 is as the purposes for DSSC or quantum dot sensitized solar cell to electrode.
10. DSSC or a quantum dot sensitized solar cell, comprises light anode, electrolyte and to electrode, it is characterized in that, described is the copper sulfide film of preparing according to the arbitrary described preparation method of claim 1～8 to electrode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409218A (en) * | 2014-11-26 | 2015-03-11 | 东华大学 | CuxS paired electrode for quantum dot-sensitized solar cells and manufacture and application thereof |
| CN105679544A (en) * | 2016-01-11 | 2016-06-15 | 上海交通大学 | Copper-manganese-germanium-sulfur counter electrode of dye-sensitized solar cell and preparation method for copper-manganese-germanium-sulfur counter electrode |
| CN109979645A (en) * | 2019-03-29 | 2019-07-05 | 合肥工业大学 | A kind of p-type copper sulfide transparent conducting film and preparation method |
| 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 |
| CN111463432A (en) * | 2020-03-25 | 2020-07-28 | 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 |
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| CN102237200A (en) * | 2011-03-04 | 2011-11-09 | 中国科学院物理研究所 | Metal sulfide counter electrode for sensitized solar cell and preparation method thereof |
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| CN102237200A (en) * | 2011-03-04 | 2011-11-09 | 中国科学院物理研究所 | Metal sulfide counter electrode for sensitized solar cell and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409218A (en) * | 2014-11-26 | 2015-03-11 | 东华大学 | CuxS paired electrode for quantum dot-sensitized solar cells and manufacture and application thereof |
| CN105679544A (en) * | 2016-01-11 | 2016-06-15 | 上海交通大学 | Copper-manganese-germanium-sulfur counter electrode of dye-sensitized solar cell and preparation method for copper-manganese-germanium-sulfur counter electrode |
| 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 |
| CN109979645A (en) * | 2019-03-29 | 2019-07-05 | 合肥工业大学 | A kind of p-type copper sulfide transparent conducting film and preparation method |
| 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 |
| 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 |
| CN111463432A (en) * | 2020-03-25 | 2020-07-28 | 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 |
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