CN103137340B - High efficiency, low cost DSSC is to the nanocrystalline preparation method of electrode material one dimension copper indium sulphur-zinc sulfide heterojunction - Google Patents

High efficiency, low cost DSSC is to the nanocrystalline preparation method of electrode material one dimension copper indium sulphur-zinc sulfide heterojunction Download PDF

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CN103137340B
CN103137340B CN201310024874.6A CN201310024874A CN103137340B CN 103137340 B CN103137340 B CN 103137340B CN 201310024874 A CN201310024874 A CN 201310024874A CN 103137340 B CN103137340 B CN 103137340B
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cuins
solution
junctions
nanocrystalline
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CN103137340A (en
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王丹
易落新
毛丹
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Foshan Gaoming (cas) Center For New Materials
Institute of Process Engineering of CAS
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Foshan Gaoming (cas) Center For New Materials
Institute of Process Engineering of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The present invention relates to a kind of high efficiency, low cost DSSC to electrode material one dimension CuInS2The nanocrystalline preparation method of hetero-junctions of-ZnS, utilizes Cu2S-ZnS heterogeneous structural nano crystalline substance is seed, introduces indium acetate in pyrosol, produces indium ion and enters Cu2The Cu of S-ZnS hetero-junctions2S copper phase, forms CuInS2Phase; Along with time lengthening, copper sulfide gradates mutually, finally forms CuInS2-ZnS heterogeneous structural nano material. Adopt the method can make one dimension CuInS2-ZnS hetero-junctions is nanocrystalline, is different from CuInS2-ZnS solid solution, has presented extraordinary CuInS2Two phase separation structures of-ZnS, with the DSSC of its paired electrode processed, photoelectric transformation efficiency exceedes traditional platinum electrode battery. The present invention adopts the seed Cu of phase-separated state2The nanocrystalline CuInS that is transformed into of S-ZnS hetero-junctions2-ZnS, has avoided CuInS2-ZnS's is common molten. Add the condition such as mode, reaction time by what change indium acetate, can realize very simply the CuInS to heterogeneous structural nano crystalline substance2Phase and the size of ZnS phase and the regulation and control of pattern. This method technological process is simple, controllability is strong.

Description

High efficiency, low cost DSSC is to the nanocrystalline preparation method of electrode material one dimension copper indium sulphur-zinc sulfide heterojunction
Technical field
The present invention relates to the preparation method of copper indium sulphur-zinc sulphide, specifically relate to a kind of dyestuff of high efficiency, low costThe nanocrystalline preparation method of hetero-junctions to electrode material one dimension copper indium sulphur-zinc sulphide of sensitization solar battery.
Background technology
DSSC adopts platinum as to electrode material, still due to platinum content rareness in the earth's crust, andAnd smelt difficulty, thereby cost is higher, becomes the major reason that dye-sensitized cell can not large-scale production. By inorganic halfDSSC prepared by conductor material to electrode, due at I-/I3-Electrolyte carries out the process of electrical conductivityIn there is the catalytic capability higher than platinum, become one of replacer of platinum electrode material. And inorganic semiconductor material is made and receivedRice material, is scattered in solvent, makes film both reduced energy consumption by the mode of printing, and method is simple, can fall to a great extentLow cost, and can prepare large area film, be conducive to large-scale production.
That prepared by the present invention is one-dimensional inorganic semiconductor CuInS2-ZnS heterojunction nanometer material, wherein CuInS2With ZnS allHave at I-/I3 -Electrolyte carries out the catalytic activity in the process of electrical conductivity, this bi-material is combined simultaneously, produces, also there are two kinds of different material composition heterojunction boundaries that produce in raw cooperative effect, gives two kinds of semi-conducting materials each in additionThe catalytic activity that all can not possess from single use, one dimension heterogeneous structural nano material also possesses unique electrical conductivity energy simultaneouslyPower, can further improve the performance of material.
Up to now, the synthetic of one dimension heterojunction nanometer material can be summarized in two different growth patterns: extension is rawRegular way and catalyst assisting growth method. Under epitaxially grown pattern, first form CuInS2Nanocrystal, taking it as seed extensionGrowing ZnS semiconductor, due to CuInS2Be a kind of semiconductor of cation defect, when high temperature, can absorb Zn ion and form CuInS2-The solid solution of ZnS. And catalyst assisting growth method can only be synthesized Si, Ge and SiO2Etc. simple nanowire heterojunction, Bu NengheBecome the CuInS of ternary2, do not become CuInS2-ZnS heterojunction nanometer material.
Summary of the invention
The object of the invention is to overcome the CuInS that prior art is separated in preparation2The difficulty of-ZnS nano material, carriesFor a kind of DSSC of high efficiency, low cost to electrode material one dimension CuInS2The hetero-junctions of-ZnS is nanocrystallinePreparation method.
The object of the invention is to realize by the following technical solutions:
The invention provides a kind of high efficiency, low cost DSSC to electrode material one dimension CuInS2-The nanocrystalline preparation method of hetero-junctions of ZnS. It,, for utilizing high temperature thermal decomposition method, adds Cu in high-temperature solvent2S-ZnS is heterogeneousStructure nano crystalline substance, as seed crystal, is then introduced indium acetate, and high-temperature heating produces free indium ion, enters the sulfuration of seedCopper phase, generates CuInS2Phase, forms CuInS with together with ZnS on original seed crystal2-ZnS heterojunction structure nanocrystalline. SpecificallyComprise following step:
1) acetylacetone copper is dissolved in lauryl mercaptan, and heats 20-30 minutes at 190-210 DEG C;
2) by being dissolved in lauryl mercaptan with the zinc acetylacetonate of acetylacetone copper equivalent, be divided into six equal portions, point six notesEnter 1) thermal response solution in, per injection interval time is 1 hour, reacts 16-18 hours after injection;
3) by organic solvent and step 2) Cu that obtains2S-ZnS mix and blend forms solution;
4) solution step 3) being obtained is heated to 190-210 DEG C under the protection of nitrogen;
5) indium acetate is introduced in the solution that step 4) obtains, kept temperature stabilization little 190-210 DEG C of reactions 4-5Time;
6) by solution cool to room temperature, centrifugal removal supernatant, being deposited in toluene solution of obtaining used after dispersion againEthanol precipitation, centrifugal, cyclic washing twice, obtains having the CuInS of phase separation structure2-ZnS hetero-junctions is nanocrystalline, reacts formerAcetylacetone copper in material, the molar ratio of zinc acetylacetonate and indium acetate is 1 ︰ 1 ︰ 1.
The CuInS with phase separation structure of the present invention2The preparation method of-ZnS one dimension heterojunction nanometer material, stepRapid 3) organic solvent in refers to the high temperature resistant inert organic solvents such as octadecylene, diphenyl ether; The introducing side of indium acetate in step 5)Formula is the mode of disposable injection or the mode of six injections of little time-division of interval one.
The present invention adopts Cu2S-ZnS hetero-junctions is nanocrystalline as seed crystal, adopts high temperature thermal decomposition method, by indium acetateIntroduce in the pyrosol of seed crystal, produce free indium ion by pyrolysis, indium ion enters Cu2S-ZnS hetero-junctions is receivedThe copper sulfide phase of rice material, generates CuInS2Thing phase; Along with the prolongation in reaction time, copper sulfide all changes into mutually graduallyCuInS2, finally form CuInS2-ZnS heterogeneous structural nano material. Utilize the reactivity of the copper sulfide phase in seed crystal,Generate CuInS2Phase, has avoided CuInS in the past2The CuInS existing in-ZnS material2-ZnS is the shortcoming of solution structure altogether. It passes throughWhat change indium acetate adds the condition such as mode, reaction time, can very simply realize heterogeneous structural nano crystalline substanceCuInS2Phase and the size of ZnS phase and the regulation and control of pattern, can obtain respectively torch-like and long bar-shaped CuInS2-ZnS hetero-junctionsNanocrystalline. By Cu1.94S-ZnS is scattered in octadecylene, stirs and within 20 minutes, forms solution; Under the protection of nitrogen, be heated to 190DEG C, disposable introducing indium acetate in reaction system heats and within 4 hours, obtains the nanocrystalline of torch-like at 190 DEG C. WillCu1.94S-ZnS is scattered in octadecylene or in diphenyl ether, stirs and within 20 minutes, forms solution; Under the protection of nitrogen, be heated to200～210 DEG C, in reaction system, divide and be injected into indium acetate six times, every minor tick one hour then adds at 200～210 DEG CHeat 4～5 hours, obtains long bar-shaped CuInS2-ZnS hetero-junctions is nanocrystalline.
This method technological process is simple, controllability is strong.
By CuInS2-ZnS is nanocrystalline to be scattered in toluene solvant, makes the solution of 0.02mol/L, drops in FTO conduction glassGlass (the SnO of doped with fluorine2Transparent conducting glass) surface, rotary glass sheet is sprawled solution, after solution evaporation, forms uniformlyCoating; To be coated again cated electro-conductive glass and be put in tube furnace under nitrogen protection 550 DEG C of calcinings 30 minutes, and form and liveProperty to electrode. Adopt silk screen print method by TiO2Jel print is made light anode to FTO electro-conductive glass, puts into 450 DEG C of horsesNot in stove, calcine 30 minutes, naturally cooling, then optoelectronic pole is at room temperature soaked to N719 dyestuff 24 hours, wash and dry,Drip upper I-/I3 -Electrolyte, buckles CuInS2The nanocrystalline preparation of-ZnS to electrode, i.e. assembling forms dye sensitization of solar electricityPond. The both positive and negative polarity of battery is connected on electrochemical workstation to test I-V song under the illumination of simulated solar irradiation (AM-1.5)Line, can directly obtain short circuit current, open-circuit voltage and transformation efficiency.
The bar-shaped CuInS of length preparing with the present invention2-ZnS heterogeneous structural nano is brilliant in dying that electrode assembling is obtainedMaterial sensitization solar battery, its photoelectric transformation efficiency is 7.5%, and under same test condition, traditional platinum obtains electrode assemblingCell photoelectric conversion efficiency be 7.1%. Therefore, adopt the CuInS that originally delivers preparation2The nanocrystalline conduct of-ZnS, can to electrodeObviously promote the photoelectric transformation efficiency of DSSC.
Brief description of the drawings
Fig. 1 is the CuInS of the torch-like prepared of EXAMPLE l2The transmission electron microscope photo of the heterogeneous structural nano crystalline substance of-ZnS.
Fig. 2 is the bar-shaped CuInS of length prepared by embodiment 22The SEM of the heterogeneous structural nano crystalline substance of-ZnSPhoto.
Fig. 3 is the bar-shaped CuInS of length prepared by embodiment 22The transmission electron microscope of the heterogeneous structural nano crystalline substance of-ZnSPhoto.
Fig. 4 is the bar-shaped CuInS of length prepared by embodiment 32The transmission electron microscope of the heterogeneous structural nano crystalline substance of-ZnSPhoto.
Fig. 5 is the bar-shaped CuInS of length prepared by embodiment 32The solar cell of the brilliant material of heterogeneous structural nano of-ZnSThe battery efficiency contrast to electrode to electrode and traditional platinum.
EXAMPLE l,
Acetylacetone copper is dissolved in to lauryl mercaptan, is placed in there-necked flask. Electric heating cover is heated to rapidly 190 DEG C. SubsequentlyBe incubated 20 minutes. To be scattered in lauryl mercaptan solvent with the zinc acetylacetonate of acetylacetone copper equivalent, be divided into six parts, divide sixInferior being injected in above-mentioned reaction solution, be 1 hour each interval time, after injection, keeping the temperature of reaction is 190 DEG C,Maintain 16 hours.
By Cu obtained above1.94S-ZnS is scattered in octadecylene, stirs and within 20 minutes, forms solution; In the protection of nitrogenUnder be heated to 190 DEG C, disposable introducing indium acetate in reaction system heats 4 hours at 190 DEG C; The solution centrifugal obtainingRemove supernatant, be deposited in toluene solution disperse after again by ethanol precipitation, centrifugal, cyclic washing twice, obtains torch-likeThere is the CuInS of phase separation structure2-ZnS hetero-junctions is nanocrystalline.
Acetylacetone copper in reaction raw materials, the molar ratio of zinc acetylacetonate and indium acetate is 1 ︰ 1 ︰ 1.
Embodiment 2
Acetylacetone copper is dissolved in to lauryl mercaptan, is placed in there-necked flask. Electric heating cover is heated to rapidly 210 DEG C. SubsequentlyBe incubated 30 minutes. To be scattered in lauryl mercaptan solvent with the zinc acetylacetonate of acetylacetone copper equivalent, be divided into six parts, divide sixInferior being injected in above-mentioned reaction solution, be 1 hour each interval time, after injection, keeping the temperature of reaction is 210 DEG C,Maintain 18 hours.
By Cu obtained above1.94S-ZnS is scattered in octadecylene, stirs and within 20 minutes, forms solution; In the protection of nitrogenUnder be heated to 210 DEG C, in reaction system, point be injected into indium acetate six times, every minor tick one hour, then heating at 210 DEG C5 hours; The solution centrifugal obtaining is removed supernatant, is deposited in toluene solution and precipitates with ethanol after dispersion again, centrifugal, repeatedly washesWash twice, obtain the long bar-shaped CuInS with phase separation structure2-ZnS hetero-junctions is nanocrystalline.
Acetylacetone copper in reaction raw materials, the molar ratio of zinc acetylacetonate and indium acetate is 1 ︰ 1 ︰ 1.
Embodiment 3
Acetylacetone copper is dissolved in to lauryl mercaptan, is placed in there-necked flask. Electric heating cover is heated to rapidly 200 DEG C. SubsequentlyBe incubated 25 minutes. To be scattered in lauryl mercaptan solvent with the zinc acetylacetonate of acetylacetone copper equivalent, be divided into six parts, divide sixInferior being injected in above-mentioned reaction solution, be 1 hour each interval time, after injection, keeping the temperature of reaction is 200 DEG C,Maintain 17 hours.
By Cu obtained above1.94S-ZnS is scattered in diphenyl ether, stirs and within 20 minutes, forms solution; In the protection of nitrogenUnder be heated to 200 DEG C, in reaction system, point be injected into indium acetate six times, every minor tick one hour, then heating at 200 DEG C4 hours; The solution centrifugal obtaining is removed supernatant, is deposited in toluene solution and precipitates with ethanol after dispersion again, centrifugal, repeatedly washesWash twice, obtain the long bar-shaped CuInS with phase separation structure2-ZnS hetero-junctions is nanocrystalline.
Acetylacetone copper in reaction raw materials, the molar ratio of zinc acetylacetonate and indium acetate is 1 ︰ 1 ︰ 1.
By CuInS2-ZnS is nanocrystalline to be scattered in toluene solvant, makes the solution of 0.02mol/L, drops in FTO conduction glassGlass surface, rotary glass sheet is sprawled solution, forms uniform coating after solution evaporation; To be coated again cated electro-conductive glassBe put in tube furnace under nitrogen protection 550 DEG C of calcinings 30 minutes, form active in electrode. Employing silk screen print method willTiO2Jel print is made light anode to FTO electro-conductive glass, puts into 450 DEG C of Muffle furnaces and calcines 30 minutes, naturally cooling, soAfter optoelectronic pole is at room temperature soaked to N719 dyestuff 24 hours, wash and dry, drip upper I-/I3 -Electrolyte, buckles CuInS2-The nanocrystalline preparation of ZnS to electrode, assembling form DSSC. The both positive and negative polarity of battery is connected to electrochemistryOn work station, test I-V curve under the illumination of simulated solar irradiation (AM-1.5), can directly obtain short circuit current, open circuit electricityPress and transformation efficiency.
The bar-shaped CuInS of length preparing with the present embodiment2The brilliant conduct of-ZnS heterogeneous structural nano obtains electrode assemblingDSSC, its photoelectric transformation efficiency is 7.5%. As a comparison, under same test condition, with traditional platinumThe cell photoelectric conversion efficiency that electrode assembling is obtained is 7.1%.

Claims (1)

  1. A DSSC to electrode material one dimension CuInS2The nanocrystalline preparation side of hetero-junctions of-ZnSMethod, comprises the steps:
    1) acetylacetone copper is dissolved in lauryl mercaptan, and heats 20-30 minute at 190-210 DEG C;
    2) by being dissolved in lauryl mercaptan with the zinc acetylacetonate of acetylacetone copper equivalent, be divided into six equal portions, point six injections 1)Thermal response solution in, per injection interval time is 1 hour, reacts 16-18 hour after injection;
    3) by diphenyl ether and step 2) the Cu2S-ZnS mix and blend that obtains forms solution;
    4) by step 3) solution that obtains is heated to 190-210 DEG C under the protection of nitrogen;
    5) indium acetate is introduced to step 4) in the solution that obtains, keep temperature stabilization at 190-210 DEG C of reaction 4-5 hour; Wherein,In reaction system, divide and be injected into indium acetate six times, every minor tick one hour;
    6) by solution cool to room temperature, centrifugal removal supernatant, being deposited in toluene solution of obtaining used ethanol after dispersion againPrecipitation, centrifugal, cyclic washing twice, obtains having the bar-shaped CuInS of length of phase separation structure2-ZnS hetero-junctions is nanocrystalline, anti-Answer acetylacetone copper in raw material, the molar ratio of zinc acetylacetonate and indium acetate is 1 ︰ 1 ︰ 1;
    By prepared CuInS2-ZnS hetero-junctions is nanocrystalline to be scattered in toluene solvant, makes the solution of 0.02mol/L, drops inThe surface of FTO electro-conductive glass, rotary glass sheet is sprawled solution, forms uniform coating after solution evaporation; To be coated with again paintingThe electro-conductive glass of layer is put in tube furnace under nitrogen protection 550 DEG C of calcinings 30 minutes, forms actively in electrode, adopts silk screenPrint process is by TiO2Jel print is made light anode to FTO electro-conductive glass, and put into 450 DEG C of Muffle furnaces and calcine 30 minutes, fromSo cooling, then optoelectronic pole is at room temperature soaked to N719 dyestuff 24 hours, wash and dry, drip upper I-/I3-Electrolyte, bucklesDescribed CuInS2The nanocrystalline preparation of-ZnS hetero-junctions to electrode, assembling form DSSC, its opto-electronic conversionEfficiency is 7.5%.
CN201310024874.6A 2013-01-23 2013-01-23 High efficiency, low cost DSSC is to the nanocrystalline preparation method of electrode material one dimension copper indium sulphur-zinc sulfide heterojunction Expired - Fee Related CN103137340B (en)

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CN109777400B (en) * 2019-01-28 2022-02-08 山东师范大学 Non-toxic Cu2S/ZnS core/shell quantum dot and preparation method thereof
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CN101830445A (en) * 2009-12-15 2010-09-15 河南大学 Novel method for synthetizing inorganic nanocrystal by taking acetylacetone as raw material
CN102086396A (en) * 2010-11-25 2011-06-08 华北电力大学 Preparation method and application in luminescent element thereof of CuInS2-ZnS/ZnSe/ZnS semiconductor quantum dots with core-shell structure

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