CN110112001B - TiC/Cu pretreated by nitric acid2S composite counter electrode, preparation method and application thereof - Google Patents
TiC/Cu pretreated by nitric acid2S composite counter electrode, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 238000000224 chemical solution deposition Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 68
- 238000005406 washing Methods 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- 239000002096 quantum dot Substances 0.000 description 36
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 31
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 25
- 238000002791 soaking Methods 0.000 description 24
- 238000000861 blow drying Methods 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- 229910052573 porcelain Inorganic materials 0.000 description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 238000010306 acid treatment Methods 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 229920001021 polysulfide Polymers 0.000 description 11
- 239000005077 polysulfide Substances 0.000 description 11
- 150000008117 polysulfides Polymers 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 10
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 229910010067 TiC2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 239000012154 double-distilled water Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical class [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
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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
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- Engineering & Computer Science (AREA)
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Abstract
A titanium sheet substrateTiC/Cu pretreated by nitric acid and prepared by three-step in-situ technology2An S composite counter electrode, a preparation method and application thereof as a counter electrode in preparation of a solar cell belong to the technical field of solar cells. Firstly, sintering at 500-600 ℃ in an oxygen atmosphere to prepare TiO2Sintering the film at 900-1000 ℃ in the atmosphere of mixed gas of argon, hydrogen and methane to obtain TiO2Converting into TiC to obtain a Ti/TiC film; the TiC is treated by nitric acid to make the surface rough, and the specific surface area of the TiC surface is increased; finally depositing Cu by chemical bath deposition2S, washing with distilled water to obtain TiC/Cu2And S is combined with a counter electrode. The method has simple preparation process, easy operation and low cost, and ensures that Cu is prepared2The coverage of S on the TiC sample with the rough surface is larger, the catalytic activity of a counter electrode can be fully improved, the photoelectric conversion efficiency is improved, and the method is suitable for a sensitized solar cell.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to TiC/Cu pretreated by nitric acid and prepared on a titanium sheet substrate through a three-step in-situ technology2An S composite counter electrode, a preparation method and application of the S composite counter electrode as a counter electrode in preparation of solar cells.
Background
The development of solar cells has entered the research stage of the third generation of solar cells, namely sensitized solar cells, including dye-sensitized solar cells, quantum dot sensitized solar cells, organic polymer solar cells, perovskite solar cells, and the like. The quantum dot sensitized solar cell has the advantages of exciton multiplication effect, adjustable band gap and the like, and is widely concerned. Research has been mainly focused over the last decade on the development of new quantum dots (CdTe, CdSe) with high light absorption and appropriate energy gap (1.4eV), and electrolytes (S) with efficient redox couples2-/Sn 2-). The development and research of new counter electrodes has also become popular in recent years, focusing mainly on the metal sulfur selenium compounds (PbS, CoS, CuS, Cu)2S andPbSe， CoSe，Cu2se, CuSe, etc.).
The ideal counter electrode should have three conditions: (1) the electrode itself has excellent conductivity; (2) the electrode has high catalytic activity to the reduction reaction of the electrolyte; (3) the electrode has good stability in electrolyte. The single-component counter electrode cannot well meet the three requirements, so that the development of the composite electrode becomes a hotspot. The composite electrode can combine the excellent performances of the two materials, thereby better improving the performance of the battery. Such as: composite counter electrode RGO/Cu2The S has excellent conductive performance of RGO and Cu2S high-efficiency electrocatalytic activity. Therefore, excellent conductivity of TiC and Cu are considered2S constructs a composite electrode with high catalytic activity to the electrolyte, and optimizes the performance of the counter electrode, thereby improving the efficiency of the quantum dot sensitized solar cell.
However, there are also disadvantages to ex situ preparation of composite electrode materials, which tend to result in poor contact with the FTO or other substrate, resulting in reduced performance. To overcome this disadvantage of poor contact caused by ex situ preparation, it is also a hot direction to prepare composite materials based on direct growth of the substrate. The TiC in-situ synthesis method mainly comprises a high-temperature C reduction method, a gas-phase reaction method, a methane high-temperature carbonization method and the like. Due to the limitation of preparation cost and the constraint of conditions, the TiC is directly prepared on the Ti sheet by adopting a methane high-temperature carbonization method.
However, the direct growth preparation material also has the defect that the specific area is too low, so that the catalytic activity of the counter electrode is too low. In order to further obtain a counter electrode with high catalytic activity, the substrate or the sample is directly treated to obtain a larger specific surface area, so as to promote the catalytic reaction of the counter electrode on the electrolyte. Such as: the counter electrode of the brass substrate is pretreated with hydrochloric acid, so that the surface is rough and the surface area is increased; the counter electrode of the titanium substrate is treated by the same hydrochloric acid to obtain the porous titanium substrate, so that the surface area of the electrode is increased. Therefore, TiC with rough surface is obtained by nitric acid treatment by utilizing the characteristic that TiC is slightly soluble in nitric acid, so that the surface Cu is improved2The growth area of S is increased to obtain larger electrocatalytic activity, and the efficiency of the quantum dot sensitized solar cell is improved.
Object of the Invention
The invention aims to: in order to overcome the defect that the specific surface area of the smooth surface of TiC is small, the TiC/Cu pretreated by nitric acid is provided2An S composite counter electrode, a preparation method and application of the S composite counter electrode as a counter electrode in preparation of solar cells.
The invention relates to TiC/Cu pretreated by nitric acid2The preparation method of the S composite counter electrode is characterized by comprising the following steps: firstly, placing a titanium sheet in a tube furnace, heating to 500-600 ℃ at a heating rate of 3-6 ℃/min in an oxygen atmosphere, and sintering for 1.5-3 h, thereby preparing a layer of TiO on the surface of the titanium sheet2(ii) a Cooling to room temperature, heating to 900-1000 ℃ at a heating rate of 3-6 ℃/min in a mixed gas atmosphere of 90%, 1% and 9% by mass of argon, hydrogen and methane, respectively, sintering for 1.5-3 h, and removing TiO on the surface of the titanium sheet2Converting into TiC; after cooling to room temperature again, putting the titanium sheet with TiC on the surface into concentrated nitric acid (the mass fraction is 65%) for surface treatment, wherein the treatment time is 15-60 min; finally depositing Cu on the titanium sheet with the surface treated and the surface provided with TiC by using a chemical bath deposition method2S, depositing for 3-6 h, and cleaning with distilled water to obtain TiC/Cu2S is a composite counter electrode; wherein TiC and Cu2The thickness ranges of S are 500 nm-1 μm and 200-500 nm respectively.
The solution used in the chemical bath deposition method is CuSO4、Na2S2O3Mixing with glacial acetic acid to obtain water solution, and adding CuSO4The concentration of (A) is 0.03-0.06M, Na2S2O3The concentration of (A) is 0.1-0.3M, and the volume of glacial acetic acid added in each 100mL of mixed aqueous solution is 0.1-0.3 mL;
the chemical bath deposition method comprises the steps of preparing the solution in a reaction vessel, vertically placing a titanium sheet with TiC on the surface after surface treatment into the reaction vessel, sealing the titanium sheet with a preservative film, placing the titanium sheet into a water bath kettle at the temperature of 20-30 ℃, heating the titanium sheet to the temperature of 60-80 ℃, and depositing the titanium sheet for 3-5 hours, so that TiC/Cu is obtained on the titanium sheet2And S is combined with a counter electrode.
The invention can utilize TiCThe TiC surface is treated by the concentrated nitric acid with the characteristic of dissolving in the concentrated nitric acid, so that the specific surface area of the TiC surface is increased, and more Cu can be deposited subsequently2S participates in the reduction process of polysulfide electrolyte, and the catalytic activity of the counter electrode is improved, so that the efficiency of the quantum dot sensitized solar cell is improved.
The invention prepares TiC/Cu by a three-step method2S composite counter electrode, i.e. first passing through TiO2Preparing TiC, treating with nitric acid to make TiC surface rough, and finally depositing Cu2And S. Simple preparation process, easy operation and low cost, and ensures that Cu is in a pure state2The S has larger coverage on the rough surface of TiC, can fully improve the catalytic activity of a counter electrode, improves the photoelectric conversion efficiency, and is suitable for a sensitized solar cell.
Drawings
FIG. 1: the structure of the solar cell prepared by the invention is shown schematically;
FIG. 2: photocurrent density-voltage (J-V) curves of the assembled solar cells of the present invention;
example 1, example 2, example 3, example 4 and example 5 correspond to curve 1, curve 2, curve 3, curve 4 and curve 5, respectively, and illustrate TiC/Cu prepared in example 32And the S composite counter electrode is an optimal condition.
Detailed Description
Example 1
Preparation of Ti/TiO2Film formation: firstly, ultrasonically washing a Ti sheet, and ultrasonically washing the Ti sheet for 15 minutes respectively by using a detergent, distilled water, acetone, isopropanol and ethanol; reproducing Ti/TiO2The film comprises the following specific processes: the washed Ti pieces (thickness: 2 μm) were cut into small pieces having a length of 2cm and a width of 2cm with scissors, and then placed in a small porcelain boat. The small porcelain boat is placed in a tube furnace, and the vacuum pump and oxygen are repeatedly used for 3 times to ensure that the air in the tube furnace is fully exhausted and simultaneously filled with oxygen atmosphere. Heating to 550 deg.C at a rate of 5 deg.C/min, maintaining for 2h, and cooling to room temperature at a rate of 5 deg.C/min to obtain Ti/TiO2A film.
Preparing a TiC film: ti prepared in the way is used for being treatedTiO2The film is placed in a small porcelain boat, then the small porcelain boat is placed in a tube furnace, and the vacuum pump and mixed gas (argon gas: hydrogen gas: methane mass fraction ratio is 90%: 1%: 9%) are utilized to repeatedly pump and inflate for 3 times respectively so as to ensure that the air in the tube furnace is fully exhausted and simultaneously the atmosphere of the mixed gas is filled. Raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then reducing the temperature to room temperature at the rate of 5 ℃/min, thereby obtaining the TiC film on the titanium sheet. Wherein the thickness of the TiC film is 700 nm.
Acid treatment of the TiC film: and (2) putting 10mL of concentrated nitric acid (mass fraction is 68%) into a 25mL beaker, placing the obtained TiC film in the beaker, soaking for 15min, taking out the obtained sample, washing with deionized water, and drying to obtain the TiC with the rough surface after acid treatment.
Preparation of TiC/Cu2S composite counter electrode: mixing CuSO4、Na2S2O3Glacial acetic acid was dissolved in 100mL water in a 250mL beaker and the solution was mixed with CuSO4Has a concentration of 0.05M, Na2S2O3The concentration of (A) is 0.2M, the volume of glacial acetic acid added is 0.2mL, and the Cu deposit is obtained after even stirring2S precursor solution. Vertically placing the titanium sheet with TiC on the surface after acid treatment into the reaction vessel, sealing with a preservative film, placing into a 25 ℃ water bath kettle, heating to 70 ℃, depositing for 4h, and obtaining Cu on TiC2S, thus preparing TiC/Cu2And S is combined with a counter electrode. Cu2The thickness of S was 300 nm.
Preparing an FTO/TiO2/CdS/CdSe/ZnSe quantum dot sensitized photo-anode: taking 0.525g of titanium potassium oxalate, 22.5mL of diethylene glycol and 7.5mL of water, ultrasonically dissolving, placing the FTO and the solution in a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 180 ℃; after the reaction is finished and cooled to room temperature, the reaction product is washed by double distilled water to obtain FTO/TiO2A film. Mixing FTO/TiO2The film is loaded with 0.1M Cd (Ac)2Soaking in methanol solution for 2min, taking out, washing with methanol, and blow-drying; after adding 0.1M Na2S, soaking in a methanol solution for 2min, taking out, washing with methanol, and blow-drying; repeating the above process for 5 times to obtain CdS quantum dot loaded TiO2. TiO loaded with CdS quantum dots2Placing in a container containing 0.1M Cd (Ac)2，0.1M Na2SeSO3，0.2M N(CH2COONa)3According to the volume ratio of 1: 1: 1 in 150mL of aqueous solution, standing at 25 ℃ in a dark state for 3h to obtain CdS/CdSe quantum dot-loaded TiO2. Wherein 0.1M Na2SeSO3The solution is prepared by dissolving 0.1mol selenium powder and 0.016mol Na2SO3Heating and refluxing the mixture for 3 hours at 99 ℃ in 50mL of water. TiO loaded with CdS/CdSe quantum dots2Adding 0.1M Zn (Ac)2Soaking in water solution for 2min, taking out, washing with methanol, and blow-drying; soaking in 0.1M NaHSe aqueous solution for 2min, taking out, washing with methanol, blow-drying, and repeating the above steps for 5 times to obtain FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photoanode, wherein CdS/CdSe/ZnSe is the QD sensitizer described in figure 1. Wherein the 0.1M aqueous solution of NaHSe is prepared by adding 0.035mol of NaBH4And 0.1mol selenium powder in 50mL water in N2Stirring for 30min under atmosphere.
Assembling the solar cell: with the above FTO/TiO2the/CdS/CdSe/ZnSe is used as a photo-anode, and the prepared TiC/Cu2S is a counter electrode, ZnSe and Cu2The S layers were placed opposite each other with a distance between the photo-anode and the counter electrode of 18 μm. In the solar cell assembled by the sandwich structure as shown in FIG. 1, 1-2 drops of polysulfide electrolyte solution (polysulfide is Na) is injected between the photo-anode and the counter electrode by a syringe2S·9H2O, S, KOH mixing with water solution of Na2S·9H2O, S, KOH at concentrations of 2M, 2M and 0.2M, respectively), the cells were sealed with epoxy resin.
And (3) carrying out performance test on the packaged solar cell: recording the photocurrent density-voltage (J-V) curve of the cell by an electrochemical workstation, wherein a 500W xenon lamp is adopted as a light source, and the light intensity of incident light is 100mW/cm2Plus a filter of AM 1.5. The activity of the battery is controlled to be 0.19625cm by the mask plate2. TiC/Cu is obtained by calculation according to a photocurrent density-voltage (J-V) curve2The short-circuit current (Jsc) of the cell in which the S film was a photocathode was 15.54mA/cm2The open circuit voltage (Voc) was 0.56V, the Fill Factor (FF) was 0.32, and the Photoelectric Conversion Efficiency (PCE) was 2.82%.
Example 2
Preparation of Ti/TiO2Film formation: firstly, ultrasonically washing a Ti sheet, and ultrasonically washing the Ti sheet for 15 minutes respectively by using a detergent, distilled water, acetone, isopropanol and ethanol; reproducing Ti/TiO2The film comprises the following specific processes: the washed Ti pieces (thickness: 2 μm) were cut into small pieces having a length of 2cm and a width of 2cm with scissors, and then placed in a small porcelain boat. The small porcelain boat is placed in a tube furnace, and the vacuum pump and oxygen are repeatedly used for 3 times to ensure that the air in the tube furnace is fully exhausted and simultaneously filled with oxygen atmosphere. Heating to 550 deg.C at a rate of 5 deg.C/min, maintaining for 2h, and cooling to room temperature at a rate of 5 deg.C/min to obtain Ti/TiO2A film.
Preparing a TiC film: mixing the above prepared Ti/TiO2The film is placed in a small porcelain boat, then the small porcelain boat is placed in a tube furnace, and the vacuum pump and mixed gas (argon gas: hydrogen gas: methane mass fraction ratio is 90%: 1%: 9%) are utilized to repeatedly pump and inflate for 3 times respectively so as to ensure that the air in the tube furnace is fully exhausted and simultaneously the atmosphere of the mixed gas is filled. Raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then reducing the temperature to room temperature at the rate of 5 ℃/min, thereby obtaining the TiC film on the titanium sheet. Wherein the thickness of the TiC film is 700 nm.
Acid treatment of the TiC film: and (2) putting 10mL of concentrated nitric acid (mass fraction is 68%) into a 25mL beaker, placing the obtained TiC film in the beaker, soaking for 30min, taking out the obtained sample, washing with deionized water, and drying to obtain the TiC with the rough surface after acid treatment.
Preparation of TiC/Cu2S composite counter electrode: mixing CuSO4、Na2S2O3Glacial acetic acid was dissolved in 100mL water in a 250mL beaker and the solution was mixed with CuSO4Has a concentration of 0.05M, Na2S2O3The concentration of (A) is 0.2M, the volume of glacial acetic acid added is 0.2mL, and the Cu deposit is obtained after even stirring2S precursor solution. Vertically placing the titanium sheet with TiC on the surface after acid treatment into the reaction vessel, sealing with a preservative film, placing into a 25 ℃ water bath kettle, heating to 70 ℃, and depositing4h, obtaining Cu on TiC2S, thus preparing TiC/Cu2And S is combined with a counter electrode. Cu2The thickness of S was 300 nm.
Preparation of FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photo-anode: taking 0.525g of titanium potassium oxalate, 22.5mL of diethylene glycol and 7.5mL of water, ultrasonically dissolving, placing the FTO and the solution in a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 180 ℃; after the reaction is finished and cooled to room temperature, the reaction product is washed by double distilled water to obtain FTO/TiO2A film. Mixing FTO/TiO2The film is loaded with 0.1M Cd (Ac)2Soaking in methanol solution for 2min, taking out, washing with methanol, and blow-drying; after adding 0.1M Na2S, soaking in a methanol solution for 2min, taking out, washing with methanol, and blow-drying; repeating the above process for 5 times to obtain CdS quantum dot loaded TiO2. TiO loaded with CdS quantum dots2Placing in a container containing 0.1M Cd (Ac)2，0.1M Na2SeSO3，0.2M N(CH2COONa)3According to the volume ratio of 1: 1: 1 in 150mL of aqueous solution, standing at 25 ℃ in a dark state for 3h to obtain CdS/CdSe quantum dot-loaded TiO2. Wherein 0.1M Na2SeSO3The solution is prepared by dissolving 0.1mol selenium powder and 0.016mol Na2SO3Heating and refluxing the mixture for 3 hours at 99 ℃ in 50mL of water. TiO loaded with CdS/CdSe quantum dots2Adding 0.1M Zn (Ac)2Soaking in water solution for 2min, taking out, washing with methanol, and blow-drying; soaking in 0.1M NaHSe aqueous solution for 2min, taking out, washing with methanol, blow-drying, and repeating the above steps for 5 times to obtain FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photoanode, wherein CdS/CdSe/ZnSe is the QD sensitizer described in figure 1. Wherein the 0.1M aqueous solution of NaHSe is prepared by adding 0.035mol of NaBH4And 0.1mol selenium powder in 50mL water in N2Stirring for 30min under atmosphere.
Assembling the solar cell: with the above FTO/TiO2the/CdS/CdSe/ZnSe is used as a photo-anode, and the prepared TiC/Cu2S is a counter electrode, ZnSe and Cu2The S layers were placed opposite each other with a distance between the photo-anode and the counter electrode of 18 μm. The solar cell is assembled by a sandwich structure as shown in FIG. 1, and 1-2 drops of polysulfide is injected between the photo-anode and the counter electrode by an injectorElectrolyte solution of compound (polysulfide Na)2S·9H2O, S, KOH mixing with water solution of Na2S·9H2O, S, KOH at concentrations of 2M, 2M and 0.2M, respectively), the cells were sealed with epoxy resin.
And (3) carrying out performance test on the packaged solar cell: recording the photocurrent density-voltage (J-V) curve of the cell by an electrochemical workstation, wherein a 500W xenon lamp is adopted as a light source, and the light intensity of incident light is 100mW/cm2Plus a filter of AM 1.5. The activity of the battery is controlled to be 0.19625cm by the mask plate2. TiC/Cu is obtained by calculation according to a photocurrent density-voltage (J-V) curve2The short-circuit current (Jsc) of the cell assembled with the S film as a photocathode was 16.35mA/cm2The open circuit voltage (Voc) was 0.57V, the Fill Factor (FF) was 0.36, and the Photoelectric Conversion Efficiency (PCE) was 3.31%.
Example 3
Preparation of Ti/TiO2Film formation: firstly, ultrasonically washing a Ti sheet, and ultrasonically washing the Ti sheet for 15 minutes respectively by using a detergent, distilled water, acetone, isopropanol and ethanol; reproducing Ti/TiO2The film comprises the following specific processes: the washed Ti pieces (thickness: 2 μm) were cut into small pieces having a length of 2cm and a width of 2cm with scissors, and then placed in a small porcelain boat. The small porcelain boat is placed in a tube furnace, and the vacuum pump and oxygen are repeatedly used for 3 times to ensure that the air in the tube furnace is fully exhausted and simultaneously filled with oxygen atmosphere. Heating to 550 deg.C at a rate of 5 deg.C/min, maintaining for 2h, and cooling to room temperature at a rate of 5 deg.C/min to obtain Ti/TiO2A film.
Preparing a TiC film: mixing the above prepared Ti/TiO2The film is placed in a small porcelain boat, then the small porcelain boat is placed in a tube furnace, and the vacuum pump and mixed gas (argon gas: hydrogen gas: methane mass fraction ratio is 90%: 1%: 9%) are utilized to repeatedly pump and inflate for 3 times respectively so as to ensure that the air in the tube furnace is fully exhausted and simultaneously the atmosphere of the mixed gas is filled. Raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then reducing the temperature to room temperature at the rate of 5 ℃/min, thereby obtaining the TiC film on the titanium sheet. Wherein the thickness of the TiC film is 700 nm.
Acid treatment of the TiC film: and (2) putting 10mL of concentrated nitric acid (mass fraction is 68%) into a 25mL beaker, placing the obtained TiC film in the beaker, soaking for 45min, taking out the obtained sample, washing with deionized water, and drying to obtain the TiC with the rough surface after acid treatment.
Preparation of TiC/Cu2S composite counter electrode: mixing CuSO4、Na2S2O3Glacial acetic acid was dissolved in 100mL water in a 250mL beaker and the solution was mixed with CuSO4Has a concentration of 0.05M, Na2S2O3The concentration of (A) is 0.2M, the volume of glacial acetic acid added is 0.2mL, and the Cu deposit is obtained after even stirring2S precursor solution. Vertically placing the titanium sheet with TiC on the surface after acid treatment into the reaction vessel, sealing with a preservative film, placing into a 25 ℃ water bath kettle, heating to 70 ℃, depositing for 4h, and obtaining Cu on TiC2S, thus preparing TiC/Cu2And S is combined with a counter electrode. Cu2The thickness of S was 300 nm.
Preparation of FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photo-anode: taking 0.525g of titanium potassium oxalate, 22.5mL of diethylene glycol and 7.5mL of water, ultrasonically dissolving, placing the FTO and the solution in a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 180 ℃; after the reaction is finished and cooled to room temperature, the reaction product is washed by double distilled water to obtain FTO/TiO2A film. Mixing FTO/TiO2The film is loaded with 0.1M Cd (Ac)2Soaking in methanol solution for 2min, taking out, washing with methanol, and blow-drying; after adding 0.1M Na2S, soaking in a methanol solution for 2min, taking out, washing with methanol, and blow-drying; repeating the above process for 5 times to obtain CdS quantum dot loaded TiO2. TiO loaded with CdS quantum dots2Placing in a container containing 0.1M Cd (Ac)2，0.1M Na2SeSO3，0.2M N(CH2COONa)3According to the volume ratio of 1: 1: 1 in 150mL of aqueous solution, standing at 25 ℃ in a dark state for 3h to obtain CdS/CdSe quantum dot-loaded TiO2. Wherein 0.1M Na2SeSO3The solution is prepared by dissolving 0.1mol selenium powder and 0.016mol Na2SO3Heating and refluxing the mixture for 3 hours at 99 ℃ in 50mL of water. TiO loaded with CdS/CdSe quantum dots20.1M of Zn (M) is put inAc)2Soaking in water solution for 2min, taking out, washing with methanol, and blow-drying; soaking in 0.1M NaHSe aqueous solution for 2min, taking out, washing with methanol, blow-drying, and repeating the above steps for 5 times to obtain FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photoanode, wherein CdS/CdSe/ZnSe is the QD sensitizer described in figure 1. Wherein the 0.1M aqueous solution of NaHSe is prepared by adding 0.035mol of NaBH4And 0.1mol selenium powder in 50mL water in N2Stirring for 30min under atmosphere.
Assembling the solar cell: with the above FTO/TiO2the/CdS/CdSe/ZnSe is used as a photo-anode, and the prepared TiC/Cu2S is a counter electrode, ZnSe and Cu2The S layers were placed opposite each other with a distance between the photo-anode and the counter electrode of 18 μm. In the solar cell assembled by the sandwich structure as shown in FIG. 1, 1-2 drops of polysulfide electrolyte solution (polysulfide is Na) is injected between the photo-anode and the counter electrode by a syringe2S·9H2O, S, KOH mixing with water solution of Na2S·9H2O, S, KOH at concentrations of 2M, 2M and 0.2M, respectively), the cells were sealed with epoxy resin.
And (3) carrying out performance test on the packaged solar cell: recording the photocurrent density-voltage (J-V) curve of the cell by an electrochemical workstation, wherein a 500W xenon lamp is adopted as a light source, and the light intensity of incident light is 100mW/cm2Plus a filter of AM 1.5. The activity of the battery is controlled to be 0.19625cm by the mask plate2. TiC/Cu is obtained by calculation according to a photocurrent density-voltage (J-V) curve2The short-circuit current (Jsc) of a cell having an S film as a photocathode was 19.11mA/cm2The open circuit voltage (Voc) was 0.57V, the Fill Factor (FF) was 0.41, and the Photoelectric Conversion Efficiency (PCE) was 4.42%.
Example 4
Preparation of Ti/TiO2Film formation: firstly, ultrasonically washing a Ti sheet, and ultrasonically washing the Ti sheet for 15 minutes respectively by using a detergent, distilled water, acetone, isopropanol and ethanol; reproducing Ti/TiO2The film comprises the following specific processes: the washed Ti pieces (thickness: 2 μm) were cut into small pieces having a length of 2cm and a width of 2cm with scissors, and then placed in a small porcelain boat. Then the small porcelain boat is placed in a tube furnace, and a vacuum pump and oxygen gas are utilized to reactAir is pumped out and inflated for 3 times respectively to ensure that the air in the tube furnace is fully exhausted and the tube furnace is full of oxygen atmosphere. Heating to 550 deg.C at a rate of 5 deg.C/min, maintaining for 2h, and cooling to room temperature at a rate of 5 deg.C/min to obtain Ti/TiO2A film.
Preparing a TiC film: mixing the above prepared Ti/TiO2The film is placed in a small porcelain boat, then the small porcelain boat is placed in a tube furnace, and the vacuum pump and mixed gas (argon gas: hydrogen gas: methane mass fraction ratio is 90%: 1%: 9%) are utilized to repeatedly pump and inflate for 3 times respectively so as to ensure that the air in the tube furnace is fully exhausted and simultaneously the atmosphere of the mixed gas is filled. Raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then reducing the temperature to room temperature at the rate of 5 ℃/min, thereby obtaining the TiC film on the titanium sheet. Wherein the thickness of the TiC film is 700 nm.
Acid treatment of the TiC film: and (2) putting 10mL of concentrated nitric acid (mass fraction is 68%) into a 25mL beaker, placing the obtained TiC film in the beaker, soaking for 60min, taking out the obtained sample, washing with deionized water, and drying to obtain the TiC with the rough surface after acid treatment.
Preparation of TiC/Cu2S composite counter electrode: mixing CuSO4、Na2S2O3Glacial acetic acid was dissolved in 100mL water in a 250mL beaker and the solution was mixed with CuSO4Has a concentration of 0.05M, Na2S2O3The concentration of (A) is 0.2M, the volume of glacial acetic acid added is 0.2mL, and the Cu deposit is obtained after even stirring2S precursor solution. Vertically placing the titanium sheet with TiC on the surface after acid treatment into the reaction vessel, sealing with a preservative film, placing into a 25 ℃ water bath kettle, heating to 70 ℃, depositing for 4h, and obtaining Cu on TiC2S, thus preparing TiC/Cu2And S is combined with a counter electrode. Cu2The thickness of S was 300 nm.
Preparation of FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photo-anode: taking 0.525g of titanium potassium oxalate, 22.5mL of diethylene glycol and 7.5mL of water, ultrasonically dissolving, placing the FTO and the solution in a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 180 ℃; after the reaction is finished and cooled to room temperature, the reaction product is washed by double distilled water to obtain FTO/TiO2A film. Mixing FTO/TiO2The film is loaded with 0.1M Cd (Ac)2Soaking in methanol solution for 2min, taking out, washing with methanol, and blow-drying; after adding 0.1M Na2S, soaking in a methanol solution for 2min, taking out, washing with methanol, and blow-drying; repeating the above process for 5 times to obtain CdS quantum dot loaded TiO2. TiO loaded with CdS quantum dots2Placing in a container containing 0.1M Cd (Ac)2，0.1M Na2SeSO3，0.2M N(CH2COONa)3According to the volume ratio of 1: 1: 1 in 150mL of aqueous solution, standing at 25 ℃ in a dark state for 3h to obtain CdS/CdSe quantum dot-loaded TiO2. Wherein 0.1M Na2SeSO3The solution is prepared by dissolving 0.1mol selenium powder and 0.016mol Na2SO3Heating and refluxing the mixture for 3 hours at 99 ℃ in 50mL of water. TiO loaded with CdS/CdSe quantum dots2Adding 0.1M Zn (Ac)2Soaking in water solution for 2min, taking out, washing with methanol, and blow-drying; soaking in 0.1M NaHSe aqueous solution for 2min, taking out, washing with methanol, blow-drying, and repeating the above steps for 5 times to obtain FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photoanode, wherein CdS/CdSe/ZnSe is the QD sensitizer described in figure 1. Wherein the 0.1M aqueous solution of NaHSe is prepared by adding 0.035mol of NaBH4And 0.1mol selenium powder in 50mL water in N2Stirring for 30min under atmosphere.
Assembling the solar cell: with the above FTO/TiO2the/CdS/CdSe/ZnSe is used as a photo-anode, and the prepared TiC/Cu2S is a counter electrode, ZnSe and Cu2The S layers were placed opposite each other with a distance between the photo-anode and the counter electrode of 18 μm. In the solar cell assembled by the sandwich structure as shown in FIG. 1, 1-2 drops of polysulfide electrolyte solution (polysulfide is Na) is injected between the photo-anode and the counter electrode by a syringe2S·9H2O, S, KOH mixing with water solution of Na2S·9H2O, S, KOH at concentrations of 2M, 2M and 0.2M, respectively), the cells were sealed with epoxy resin.
And (3) carrying out performance test on the packaged solar cell: recording the photocurrent density-voltage (J-V) curve of the cell by an electrochemical workstation, wherein a 500W xenon lamp is adopted as a light source, and the light intensity of incident light is 100mW/cm2Optical filter with addition of AM 1.5. The activity of the battery is controlled to be 0.19625cm by the mask plate2. TiC/Cu is obtained by calculation according to a photocurrent density-voltage (J-V) curve2The short-circuit current (Jsc) of a cell having an S film as a photocathode was 17.46mA/cm2The open circuit voltage (Voc) was 0.57V, the Fill Factor (FF) was 0.44, and the Photoelectric Conversion Efficiency (PCE) was 4.34%.
Example 5 (this example is without surface treatment of TiC with concentrated nitric acid, for comparison with the present invention.)
Preparation of Ti/TiO2Film formation: firstly, ultrasonically washing a Ti sheet, and ultrasonically washing the Ti sheet for 15 minutes respectively by using a detergent, distilled water, acetone, isopropanol and ethanol; reproducing Ti/TiO2The film comprises the following specific processes: the washed Ti pieces (thickness: 2 μm) were cut into small pieces having a length of 2cm and a width of 2cm with scissors, and then placed in a small porcelain boat. The small porcelain boat is placed in a tube furnace, and the vacuum pump and oxygen are repeatedly used for 3 times to ensure that the air in the tube furnace is fully exhausted and simultaneously filled with oxygen atmosphere. Heating to 550 deg.C at a rate of 5 deg.C/min, maintaining for 2h, and cooling to room temperature at a rate of 5 deg.C/min to obtain Ti/TiO2A film.
Preparing a TiC film: mixing the above prepared Ti/TiO2The film is placed in a small porcelain boat, then the small porcelain boat is placed in a tube furnace, and the vacuum pump and mixed gas (argon gas: hydrogen gas: methane mass fraction ratio is 90%: 1%: 9%) are utilized to repeatedly pump and inflate for 3 times respectively so as to ensure that the air in the tube furnace is fully exhausted and simultaneously the atmosphere of the mixed gas is filled. Raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then reducing the temperature to room temperature at the rate of 5 ℃/min, thereby obtaining the TiC film on the titanium sheet. Wherein the thickness of the TiC film is 700 nm.
Preparation of TiC/Cu2S composite counter electrode: mixing CuSO4、Na2S2O3Glacial acetic acid was dissolved in 100mL water in a 250mL beaker and the solution was mixed with CuSO4Has a concentration of 0.05M, Na2S2O3The concentration of (A) is 0.2M, the volume of glacial acetic acid added is 0.2mL, and the Cu deposit is obtained after even stirring2S precursor solution. To carry a surface withVertically placing TiC titanium sheet into the reaction vessel, sealing with preservative film, placing into 25 deg.C water bath, heating to 70 deg.C, depositing for 4h to obtain Cu on TiC2S, thus preparing TiC/Cu2And S is combined with a counter electrode. Cu2The thickness of S was 300 nm.
Preparation of FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photo-anode: taking 0.525g of titanium potassium oxalate, 22.5mL of diethylene glycol and 7.5mL of water, ultrasonically dissolving, placing the FTO and the solution in a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 180 ℃; after the reaction is finished and cooled to room temperature, the reaction product is washed by double distilled water to obtain FTO/TiO2A film. Mixing FTO/TiO2The film is loaded with 0.1M Cd (Ac)2Soaking in methanol solution for 2min, taking out, washing with methanol, and blow-drying; after adding 0.1M Na2S, soaking in a methanol solution for 2min, taking out, washing with methanol, and blow-drying; repeating the above process for 5 times to obtain CdS quantum dot loaded TiO2. TiO loaded with CdS quantum dots2Placing in a container containing 0.1M Cd (Ac)2，0.1M Na2SeSO3，0.2M N(CH2COONa)3According to the volume ratio of 1: 1: 1 in 150mL of aqueous solution, standing at 25 ℃ in a dark state for 3h to obtain CdS/CdSe quantum dot-loaded TiO2. Wherein 0.1M Na2SeSO3The solution is prepared by dissolving 0.1mol selenium powder and 0.016mol Na2SO3Heating and refluxing the mixture for 3 hours at 99 ℃ in 50mL of water. TiO loaded with CdS/CdSe quantum dots2Adding 0.1M Zn (Ac)2Soaking in water solution for 2min, taking out, washing with methanol, and blow-drying; soaking in 0.1M NaHSe aqueous solution for 2min, taking out, washing with methanol, blow-drying, and repeating the above steps for 5 times to obtain FTO/TiO2a/CdS/CdSe/ZnSe quantum dot sensitized photoanode, wherein CdS/CdSe/ZnSe is the QD sensitizer described in figure 1. Wherein the 0.1M aqueous solution of NaHSe is prepared by adding 0.035mol of NaBH4And 0.1mol selenium powder in 50mL water in N2Stirring for 30min under atmosphere.
Assembling the solar cell: with the above FTO/TiO2the/CdS/CdSe/ZnSe is used as a photo-anode, and the prepared TiC/Cu2S is a counter electrode, ZnSe and Cu2The S layers were placed opposite each other with a distance between the photo-anode and the counter electrode of 18 μm. Root of herbaceous plantA solar cell is assembled by a sandwich structure as shown in FIG. 1, and a polysulfide electrolyte solution (polysulfide is Na) is injected between a photo-anode and a counter electrode by 1-2 drops2S·9H2O, S, KOH mixing with water solution of Na2S·9H2O, S, KOH at concentrations of 2M, 2M and 0.2M, respectively), the cells were sealed with epoxy resin.
And (3) carrying out performance test on the packaged solar cell: recording the photocurrent density-voltage (J-V) curve of the cell by an electrochemical workstation, wherein a 500W xenon lamp is adopted as a light source, and the light intensity of incident light is 100mW/cm2Plus a filter of AM 1.5. The activity of the battery is controlled to be 0.19625cm by the mask plate2. TiC/Cu is obtained by calculation according to a photocurrent density-voltage (J-V) curve2The short-circuit current (Jsc) of the cell in which the S film was a photocathode was 15.9mA/cm2The open circuit voltage (Voc) was 0.57V, the Fill Factor (FF) was 0.29, and the Photoelectric Conversion Efficiency (PCE) was 2.66%.
Claims (7)
1. TiC/Cu pretreated by nitric acid2The preparation method of the S composite counter electrode is characterized by comprising the following steps: firstly, placing a titanium sheet in a tube furnace, heating to 500-600 ℃ in an oxygen atmosphere, and sintering for 1.5-3 h, thereby preparing a layer of TiO on the surface of the titanium sheet2(ii) a Cooling to room temperature, heating to 900-1000 ℃ in a mixed gas atmosphere of 90%, 1% and 9% by mass of argon, hydrogen and methane respectively, sintering for 1.5-3 h, and removing TiO on the surface of the titanium sheet2Converting into TiC; after cooling to room temperature again, putting the titanium sheet with TiC on the surface into concentrated nitric acid with the mass fraction of 65% for surface treatment, wherein the treatment time is 15-60 min; finally depositing Cu on the titanium sheet with the surface treated and the surface provided with TiC by using a chemical bath deposition method2S, depositing for 3-6 h, and cleaning with distilled water to obtain TiC/Cu2And S is combined with a counter electrode.
2. The TiC/Cu pretreated with nitric acid of claim 12The preparation method of the S composite counter electrode is characterized by comprising the following steps: heating to 500-600 ℃ and 900-1000 ℃The speed is 3-6 ℃/min.
3. The TiC/Cu pretreated with nitric acid of claim 12The preparation method of the S composite counter electrode is characterized by comprising the following steps: TiC and Cu2The thickness ranges of S are 500 nm-1 μm and 200-500 nm respectively.
4. The TiC/Cu pretreated with nitric acid of claim 12The preparation method of the S composite counter electrode is characterized by comprising the following steps: the solution used in the chemical bath deposition method is CuSO4、Na2S2O3Mixed aqueous solution of glacial acetic acid and CuSO in the mixed aqueous solution4The concentration of (A) is 0.03-0.06M, Na2S2O3The concentration of (A) is 0.1-0.3M, and the volume of glacial acetic acid added in each 100mL of mixed aqueous solution is 0.1-0.3 mL.
5. The TiC/Cu pretreated with nitric acid of claim 42The preparation method of the S composite counter electrode is characterized by comprising the following steps: the chemical bath deposition method comprises the steps of preparing the solution in a reaction vessel, vertically placing a titanium sheet with TiC on the surface after surface treatment into the reaction vessel, sealing the titanium sheet with a preservative film, placing the titanium sheet into a water bath kettle at the temperature of 20-30 ℃, heating the titanium sheet to the temperature of 60-80 ℃, and depositing the titanium sheet for 3-5 hours, so that TiC/Cu is obtained on the titanium sheet2And S is combined with a counter electrode.
6. TiC/Cu pretreated by nitric acid2The S composite counter electrode is characterized in that: is prepared by any one of the methods of claims 1 to 5.
7. The TiC/Cu pretreated with nitric acid of claim 62The S composite counter electrode is used as a counter electrode in the preparation of solar cells.
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