CN106298247A - DSSC XS(X=Co, Ni) preparation method to electrode - Google Patents

DSSC XS(X=Co, Ni) preparation method to electrode Download PDF

Info

Publication number
CN106298247A
CN106298247A CN201610651679.XA CN201610651679A CN106298247A CN 106298247 A CN106298247 A CN 106298247A CN 201610651679 A CN201610651679 A CN 201610651679A CN 106298247 A CN106298247 A CN 106298247A
Authority
CN
China
Prior art keywords
electrode
preparation
dssc
mixed solution
conductive glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610651679.XA
Other languages
Chinese (zh)
Inventor
孙小华
汪佳丽
陈琳琳
鲍潮
郑琳杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Three Gorges University CTGU
Original Assignee
China Three Gorges University CTGU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Three Gorges University CTGU filed Critical China Three Gorges University CTGU
Priority to CN201610651679.XA priority Critical patent/CN106298247A/en
Publication of CN106298247A publication Critical patent/CN106298247A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/287—Chalcogenides
    • C03C2217/288—Sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a kind of DSSC XS(X=Co, Ni) preparation method to electrode, its step is as follows: by X (CH3COO)2`4H2O(X=Co, Ni) and thiourea be dissolved in the mixed solution of ammonia and ethanol；Becoming 50 ° after being cleaned up by FTO electro-conductive glass to be placed in in teflon-lined stainless steel cauldron, conducting surface is downward；Mixed solution is transferred to carry out in reactor solvent thermal reaction.After reaction terminates, take out electro-conductive glass, dry with ethanol purge, i.e. obtain XS(X=Co, Ni) to electrode.XS(X=Co, Ni disclosed by the invention) simple to the preparation method of electrode, manufacturing cycle is short, can carry out rapid large-area and prepare；Meanwhile, the catalysis activity height little to electrode interface charge transfer resistance of preparation, thin film has light transmission, extremely efficient improves the photoelectric transformation efficiency of DSSC.

Description

DSSC XS(X=Co, Ni) preparation method to electrode
Technical field
The invention belongs to nano material preparation technology and energy field, relate to a kind of DSSC to electrode The preparation method of material.
Background technology
Along with the sustainable growth of population in the world, the dependency of the energy is gradually deepened by people, causes lack of energy and ring The series of problems such as environment pollution occur, therefore developing reproducible clean energy resource is to alleviate world energy sources crisis and ambient pressure One of important channel and measure.The regenerative resources such as its waterpower, wind energy, geothermal energy compared by solar energy, are inexhaustible, with no Exhaust.And obtaining conveniently, cleanliness without any pollution, it uses without geographical restrictions, utilizes advantage of lower cost.Research at present and application Widest solaode is silica-based solar cell, but the complex manufacturing technology of silica-based solar cell, cost of manufacture is high, And conversion efficiency is close to theoretical boundary, further development space is limited.Therefore the solaode that development cost is low it is badly in need of. Electrode mainly by light anode, electrolyte and is formed by DSSC.Wherein, to electrode as battery just , mainly there is following effect pole: (1) is collected and transported electronics and (receive the electronics of battery external loop and pass it in electrolyte Oxidation-reduction pair)；(2) adsorbing electrolyte be catalyzed I3 −Reduction；(3) increase through light, thus improve the profit of sunlight By rate.At present, the DSSC Pt electrode that use sputtering and thermolysis process prepare general to electrode material, because of There is the advantages such as high electro catalytic activity, high conductivity and high stability for this material.But owing to Pt belongs to noble metal, Greatly improve the preparation cost of battery, and use the method for the Pt electrode of sputtering and thermal decomposition preparation to belong to highly energy-consuming work Skill, hinders the Industrialization Progress of DSSC.
Seek the concern that electrode material is increasingly subject to people of low cost.Meanwhile, transient metal sulfide has excellence Optical property, electric property and catalytic performance, thus cause the attention of researcher in field of dye-sensitized solar cells. Wherein, the step solvent-thermal method that the present invention provides is simple to technology for preparing electrode, and can prepare two kinds of differences by same technique To electrode, preparation technology is simple, with low cost, and prepared is high to electrode electro catalytic activity, has light transmission, effectively improves The photoelectric transformation efficiency of DSSC.
Summary of the invention
The invention aims to solve that existing DSSC is expensive to electrode material, be not suitable for The problem of large-scale application, it is provided that a kind of DSSC XS(X=Co, Ni) system to electrode one step solvent thermal Preparation Method.
The present invention is achieved by the following technical solutions:
Preparation mole proportioning is X (CH3COO)2·4H2O (X=Co, Ni): thiourea is 1:(1 ~ 3.0), and ammonia and ethanol body Long-pending be poured in reactor than the mixed solution for (1/10 ~ 10), FTO electro-conductive glass is put in reactor (conduct electricity towards Under), at 120 DEG C ~ 220 DEG C, react 8 ~ 24 hours, by gained FTO sample alcohol flushing, be dried to obtain electrode.
The present invention provides a kind of DSSC XS(X=Co, Ni) a step solvent thermal preparation side to electrode Method.The method is simple to operate, simple, with low cost, prepared high to electrode electro catalytic activity of preparation technology, has light transmission, Effectively improve the photoelectric transformation efficiency of DSSC.
Present invention both sexes based on some metal ions (Acidity of Aikalinity) attribute, solution pH value is by the differentiation of acidity to alkalescence Cheng Zhong, corresponding slaine can dissolve, precipitates, dissolve.Based on this, in hydro-thermal reaction, the pH value of regulation and control reaction stock solution, can shadow In Xiangshui County's thermal response, the row crystalline nucleation of target substance separates out and the change of thing phase morphology and performance.The proposition of the present invention is exactly will Cobalt, the acetate of nickel (regulate and control) wiring solution-forming under alkaline environment by ammonia, by thiourea in the hydro-thermal reaction of high temperature Hydrolysis release hydrogen ions, reduces pH value, also discharges S simultaneously2-Ion and cobalt, nickel ion form cobalt, nickel under suitable pH value Sulfide, and form the sulfide with different-shape and performance.
Accompanying drawing explanation
Fig. 1 be in embodiment 1,2 CoS, NiS to electrode and Pt the J-V curve to electrode.
Fig. 2 is the light transmission accompanying drawing of the CoS in embodiment 1.
Fig. 3 is the light transmission accompanying drawing of the NiS in embodiment 2.
Fig. 4 be the CoS in embodiment 3 to electrode and Pt the J-V curve to electrode.
Fig. 5 be the CoS in embodiment 4 to electrode and Pt the J-V curve to electrode.
Fig. 6 is the SEM accompanying drawing of the CoS in embodiment 4.
Fig. 7 is the SEM accompanying drawing of the CoS in embodiment 4.
Fig. 8 is the SEM accompanying drawing of the CoS in embodiment 4.
Fig. 9 be the NiS in embodiment 5 to electrode and Pt the J-V curve to electrode.
Figure 10 is the SEM accompanying drawing of the NiS in embodiment 5.
Figure 11 is the SEM accompanying drawing of the NiS in embodiment 5.
Figure 12 is the SEM accompanying drawing of the NiS in embodiment 5.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is further described, but is not limited thereto, every to this Inventive technique scheme is modified or equivalent, without deviating from thought and the scope of technical solution of the present invention, all should contain In protection scope of the present invention.
Embodiment 1 solvent thermal condition is that electrode preparation mole proportioning is by 18 hours prepared CoS of 180 DEG C of reactions Cobalt diacetate tetrahydrate: thiourea is 1:1.5, and ammonia and ethanol volume ratio be the mixed solution of 5:2, is poured in reactor, will FTO electro-conductive glass puts into (conducting surface is downward) in reactor, reacts 18 hours, rushed by gained FTO sample ethanol at 180 DEG C Wash, be dried to obtain electrode.
TiO2The preparation of light anode and battery performance test:
Dye-sensitized solar cell anode prepares titanium dioxide nanocrystalline thin film by cladding process, and titania slurry is by water Thermal synthesis prepares and (sees S. Ito, T. Murakami, P. Comte, P. Liska, C. Gr tzel, M. Nazeeruddin, M. Gr tzel, Thin Solid Films, 516 (2008) 4613-4619).
With N719 sensitized cells light anode, and drip redox electrolytes matter on this electrode, redox electrolytes matter Consist of: 0.1M 1-propy-3-methylimidazolium iodide (1-propyl group-3-Methylimidazole. iodine), 0.05M LiI, 0.1M GNCS, 0.03M I2, 0.5M 4-terT-butylpridine (4-tert .-butylpyridine), solvent is carbonic acid Propylene fat and the mixed solution (volume ratio is 1:1) of acetonitrile.The sulfide prepared by the present invention becomes dye sensitization to electrode assembling Solaode, test performance.
At room temperature, using 1000W simulated solar radiant xenon lamp (Oriel 91192, USA), irradiation intensity is 100W/cm2, the instrument such as electrochemical workstation, dark slide is 0.25cm by illuminating area2, electrode is assembled by gained DSSC carry out performance test, the J-V curve of gained as it is shown in figure 1, its conversion efficiency reaches 6.52%, Higher than the Pt conversion efficiency 6.44% to electrode.Light transmission is as shown in Figure 2.
Embodiment 2 solvent thermal condition is that electrode preparation mole proportioning is by 18 hours prepared NiS of 180 DEG C of reactions Four water acetic acid nickel: thiourea is 1:1.5, and ammonia and ethanol volume ratio be the mixed solution of 1:6, is poured in reactor, will FTO electro-conductive glass puts into (conducting surface is downward) in reactor, reacts 18 hours, rushed by gained FTO sample ethanol at 180 DEG C Wash, be dried to obtain electrode.
TiO2The preparation of light anode and battery performance test method and steps are with identical in example one.
Gained sample is carried out performance test gained as the DSSC assembling electrode J-V curve as shown in Figure 1.Thus can learn, its conversion efficiency reaches 6.79%, higher than the Pt conversion efficiency to electrode 6.44%.Light transmission is as shown in Figure 3.
Embodiment 3 mol ratio is Cobalt diacetate tetrahydrate: thiourea is that electrode preparation mole is joined by the CoS prepared by 1:1. Ratio is for Cobalt diacetate tetrahydrate: thiourea is 1:1, and ammonia is the mixed solution of 4:3 with ethanol volume ratio, is poured in reactor, FTO electro-conductive glass is put into (conducting surface is downward) in reactor, at 180 DEG C, reacts 18 hours, by gained FTO sample ethanol Rinse, be dried to obtain electrode.
TiO2The preparation of light anode and battery performance test method and steps are with identical in example one.
Gained sample is carried out performance test gained as the DSSC assembling electrode J-V curve as shown in Figure 4.Thus can learn, its conversion efficiency reaches 6.35%, approximates the Pt conversion efficiency to electrode 6.39%。
Embodiment 4 ammonia and ethanol volume ratio are 5:2, react 12 hours prepared CoS and electrode is prepared mole Proportioning is Cobalt diacetate tetrahydrate: thiourea is 1:1.5, and ammonia is the mixed solution of 5:2 with ethanol volume ratio, is poured into reactor In, FTO electro-conductive glass is put into (conducting surface is downward) in reactor, at 180 DEG C, reacts 12 hours, gained FTO sample is used Alcohol flushing, is dried to obtain electrode.
TiO2The preparation of light anode and battery performance test method and steps are with identical in example one.
Gained sample is carried out performance test gained as the DSSC assembling electrode J-V curve as shown in Figure 5.Thus can learn, its conversion efficiency reaches 6.35%, approximates the Pt conversion efficiency to electrode 6.44%.Pattern is as shown in Figure 6.Only changing ammonia is 4:3 and 3:4 with ethanol volume ratio, and pattern is as shown in Figure 7,8.
Embodiment 5 ammonia and ethanol volume ratio are 1:6, react 12 hours prepared NiS and electrode is prepared mole Proportioning is four water acetic acid nickel: thiourea is 1:1.5, and ammonia is the mixed solution of 1:6 with ethanol volume ratio, is poured into reactor In, FTO electro-conductive glass is put into (conducting surface is downward) in reactor, at 180 DEG C, reacts 12 hours, gained FTO sample is used Alcohol flushing, is dried to obtain electrode.
TiO2The preparation of light anode and battery performance test method and steps are with identical in example one.
Gained sample is carried out performance test gained as the DSSC assembling electrode J-V curve as shown in Figure 9.Thus can learn, its conversion efficiency reaches 4.48%, less than the Pt conversion efficiency to electrode 6.49%.Pattern is as shown in Figure 10.Only changing ammonia is 17:18 and 0:25 with ethanol volume ratio, and pattern is as shown in Figure 11,12.

Claims (2)

1. DSSC XS(X=Co, Ni) preparation method to electrode, its feature will be in, and described method step is such as Under:
Step one: by X (CH3COO)2·4H2O (X=Co, Ni), thiourea are dissolved in the mixed solution of ammonia and ethanol successively, Stirring 30min, forms uniform mixed solution；
Step 2: by the FTO electro-conductive glass that cleans up with 45°Angle is inclined in the 50ml stainless steel reaction with polytetrafluoro liner In still, and conducting surface is downward；
Step 3: transferred to by mixed solution in aforesaid reaction vessel, under the conditions of control reaction temperature is 120 DEG C ~ 220 DEG C, reacts 8 ~ 24 hours time, naturally cool to room temperature, take out the FTO electro-conductive glass being placed in inside, by washing with alcohol, be dried to obtain electricity Pole.
The DSSC NiS the most according to claim 1 preparation method to electrode, it is characterised in that on Described X (CH3COO)2`4H2O(X=Co, Ni): the mol ratio of thiourea is 1:(1 ~ 3.0), wherein ammonia with the volume ratio of ethanol is 0.1 ~ 10:1.
CN201610651679.XA 2016-08-10 2016-08-10 DSSC XS(X=Co, Ni) preparation method to electrode Pending CN106298247A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610651679.XA CN106298247A (en) 2016-08-10 2016-08-10 DSSC XS(X=Co, Ni) preparation method to electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610651679.XA CN106298247A (en) 2016-08-10 2016-08-10 DSSC XS(X=Co, Ni) preparation method to electrode

Publications (1)

Publication Number Publication Date
CN106298247A true CN106298247A (en) 2017-01-04

Family

ID=57667762

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610651679.XA Pending CN106298247A (en) 2016-08-10 2016-08-10 DSSC XS(X=Co, Ni) preparation method to electrode

Country Status (1)

Country Link
CN (1) CN106298247A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106865624A (en) * 2017-01-22 2017-06-20 温州大学 A kind of cobalt sulfide material, preparation method and its usage
CN106952731A (en) * 2017-03-01 2017-07-14 三峡大学 A kind of DSSC NiS2/CoS2To the preparation method of electrode
CN109712814A (en) * 2019-01-09 2019-05-03 东南大学 A kind of FeCo of efficient stable2S4The preparation method and application of conductive film
CN110739155A (en) * 2019-09-24 2020-01-31 广东工业大学 nickel sulfide/graphene composite film and preparation method and application thereof
CN112768251A (en) * 2020-12-25 2021-05-07 合肥工业大学 Mirror-surface-shaped cobalt sulfide counter electrode and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560013A (en) * 2013-11-07 2014-02-05 武汉大学 Dye-sensitized solar cell with sulfide counter electrode and preparation method thereof
CN104701018A (en) * 2015-01-29 2015-06-10 三峡大学 One-step solvothermal preparation method for dye-sensitized solar cell CoS counter electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560013A (en) * 2013-11-07 2014-02-05 武汉大学 Dye-sensitized solar cell with sulfide counter electrode and preparation method thereof
CN104701018A (en) * 2015-01-29 2015-06-10 三峡大学 One-step solvothermal preparation method for dye-sensitized solar cell CoS counter electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JINGHAO HUO: "Effect of ammonia on electrodeposition of cobalt sulfide and nickel sulfide counter electrodes for dye-sensitized solar cells", 《ELECTROCHIMICA ACTA》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106865624A (en) * 2017-01-22 2017-06-20 温州大学 A kind of cobalt sulfide material, preparation method and its usage
CN106952731A (en) * 2017-03-01 2017-07-14 三峡大学 A kind of DSSC NiS2/CoS2To the preparation method of electrode
CN109712814A (en) * 2019-01-09 2019-05-03 东南大学 A kind of FeCo of efficient stable2S4The preparation method and application of conductive film
CN110739155A (en) * 2019-09-24 2020-01-31 广东工业大学 nickel sulfide/graphene composite film and preparation method and application thereof
CN110739155B (en) * 2019-09-24 2021-10-19 广东工业大学 Nickel sulfide/graphene composite film and preparation method and application thereof
CN112768251A (en) * 2020-12-25 2021-05-07 合肥工业大学 Mirror-surface-shaped cobalt sulfide counter electrode and application thereof

Similar Documents

Publication Publication Date Title
CN106298247A (en) DSSC XS(X=Co, Ni) preparation method to electrode
CN106952731B (en) A kind of dye-sensitized solar cells NiS2/CoS2To the preparation method of electrode
CN104393103B (en) A kind of Cu2ZnSnS4The preparation method of semiconductive thin film and application thereof
CN102610392A (en) Metal selenide counter-electrode for dye-sensitized solar cell and preparation method of metal selenide counter-electrode
CN104911639B (en) A kind of supported silver nano net and its preparation method and application
CN111569896A (en) BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water
CN106024395B (en) A kind of Ni based on nickel foam3Se2The preparation method and applications of nano material
CN105321719A (en) Hierarchical mesoporous TiO2 prepared by taking MOF as precursor and application
CN104016405A (en) Flower-shaped mesoporous titanium dioxide material and preparation method and application thereof
CN106222685A (en) A kind of WO of photoelectrocatalysis water decomposition3the preparation method of LDH laminated film
CN103474243A (en) Preparation method for dye-sensitized solar cell counter electrode based on nickel sulfide nanosheets
CN103050289B (en) Two-sided DSSC of polyaniline transparent counter electrode base and its preparation method and application
CN108493297B (en) Preparation method of three-dimensional hollow selenium nickel sulfide nano-frame catalyst
CN104576074A (en) Preparation method for ultra-long TiO2 nanowire array thin-film photo-anode
CN108172401A (en) Dye-sensitized cell combined counter electrode and its preparation method and application
CN104701018A (en) One-step solvothermal preparation method for dye-sensitized solar cell CoS counter electrode
CN104157456B (en) High catalytic activity sulfide hybridization counter electrode for flexible dye-sensitized solar cell and preparation method thereof
CN103606463B (en) For the nano-composite counter electrode and preparation method thereof of DSSC
CN104016419A (en) Method for preparing three-dimensional flower-shaped CoS hierarchy counter electrode of dye-sensitized solar cell
CN103985547A (en) Mirror-face nickel sulfide nano-sheet counter electrode and application thereof
CN105568309A (en) Preparation method for photoelectrode of photoelectrochemical cell
CN105543889A (en) Perovskite structure oxynitride photocatalytic water splitting anode material and preparation method thereof
CN105244171B (en) A kind of fabricated in situ ZnO nano piece photo-anode film and preparation method thereof
CN106206042A (en) A kind of DSSC NiSe preparation method to electrode
CN105280389A (en) Preparation method for dye-sensitized solar cell

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170104