CN101770870A - Low-cost counter electrode for dye-sensitized solar battery - Google Patents

Low-cost counter electrode for dye-sensitized solar battery Download PDF

Info

Publication number
CN101770870A
CN101770870A CN 201010131086 CN201010131086A CN101770870A CN 101770870 A CN101770870 A CN 101770870A CN 201010131086 CN201010131086 CN 201010131086 CN 201010131086 A CN201010131086 A CN 201010131086A CN 101770870 A CN101770870 A CN 101770870A
Authority
CN
China
Prior art keywords
electrode
counter electrode
carbide
dssc
nitride
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
CN 201010131086
Other languages
Chinese (zh)
Inventor
马廷丽
武明星
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.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
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 Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN 201010131086 priority Critical patent/CN101770870A/en
Publication of CN101770870A publication Critical patent/CN101770870A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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 low-cost counter electrode and a dye-sensitized solar battery manufacturing process by utilizing the counter electrode, belonging to the technical field of green renewable energy sources; the counter electrode is characterized in that: molybdenum carbide (Mo2C), tungsten nitride (W2N), molybdenum nitride (Mo2N), vanadium carbide (VC), vanadium nitride (VN), niobium carbide (NbC), niobium nitride (NbN), and wolfram carbide (WC,W2C) are used as material of the counter electrode, inorganic crystalline material is used as bonder and is dispersed in organic solvent or aqueous solution for manufacturing slurry, and the counter electrode is manufactured by utilizing spraying, printing, blade coating methods, and the counter electrode and light anode and electrolyte are assembled into the dye-sensitized solar battery. The preparation process is simple, high temperature and high pressure do not need in the manufacturing process, the process is no toxic and environmental-protection, the electrode with high efficiency and low cost can be manufactured easily, and the process is suitable for manufacturing various dye-sensitized solar batteries.

Description

A kind of low cost of DSSC that is used for is to electrode
Technical field
The invention belongs to technical field of green regenerative energy sources, relate to a kind of low cost the making of electrode and the application in DSSC thereof.
Background technology
1991, professor Graetzel of engineering college of Swiss Confederation invented DSSC (being called for short DSC).Because it is with low cost, manufacture craft is simple, and efficient is higher, and environmental friendliness just causes worldwide research boom once coming out.DSC mainly is made up of three parts, that is: light anode normally is adsorbed with the nano-crystalline titanium dioxide film of dyestuff; To electrode, platinum electrode normally; Comprise I in addition 3 -/ I -The electrolyte of oxidation-reduction pair.Its principle is: dyestuff absorbs a photon, dyestuff is from the ground state transition to excitation state, dyestuff excitation state instability, produce a light induced electron and dyestuff cation, light induced electron can be injected into the conduction band of titanium dioxide rapidly and the loose structure by titanium dioxide reaches conductive substrates, and the external circuit of flowing through then reaches electrode.On to electrode, I 3 -The electron reduction of the external circuit of being flowed through is I -, in titanium dioxide porous membrane, the dyestuff cation is by I -Reduction realizes the regeneration of dyestuff, finishes the entire circuit circulation.This shows to electrode it is the important component part of DSC, mainly is to do electrode with platinum at present.Though the platinum electrode superior performance still costs an arm and a leg, and the reserves of platinum are very limited, therefore be badly in need of seeking the substitution material of platinum.
Summary of the invention
At the problems referred to above, the invention provides a kind of electrode material of alternative platinum, and propose a kind of simply to the preparation technology of electrode and with this to electrode make efficiency height, DSSC cheaply.For achieving the above object, technical scheme of the present invention is eka-platinium compound powder, inorganic compound adhesive, dispersant to be dispersed in the organic solvent or the aqueous solution be mixed with slurry, and utilize methods such as spraying, blade coating, printing to be made into electrode, and then be assembled into DSSC.To electrode material can be a kind of class platinum compounds or the mixture of more than one class platinum compounds, or the mixture of the above material and electrode materials such as Pt, C.
Described class platinum compounds comprises molybdenum carbide (Mo 2C), tungsten nitride (W 2N), molybdenum nitride (Mo 2N), vanadium carbide (VC), vanadium nitride (VN), niobium carbide (NbC), niobium nitride (NbN), tungsten carbide (WC or W 2C), its particle diameter is between 2nm-800 μ m.The electrode of this eka-platinium material preparation is the oxidation-reduction pair in the related electrolyte in can the catalysis DSSC, as I 3 -/ I -, Br 3 -/ Br -And other oxidation-reduction pair.
Above-mentioned inorganic compound adhesive can be titanium dioxide, aluminium oxide, tin ash, silicon dioxide, zinc oxide, cupric oxide, nickel oxide, magnesium sulfate, calcium sulfate, magnesium hydroxide, in barium sulfate, the iron oxide one or more mix, and its particle diameter is between 2nm-800 μ m.
Above-mentioned dispersant can be one or more the mixed liquor in polyethylene glycol, TritonX 100, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, the fatty acid polyethylene glycol ester.
Except that can utilizing spraying process, print process, knife coating, also can use electrochemical deposition method, galvanoplastic, pyrolysismethod, sputtering method to the preparation method of electrode.
This technical skill not only can substitute platinum electrode, reduces the cost of manufacture of electrode significantly, and can also obtain very high photoelectric current and open circuit voltage and photoelectric conversion efficiency, makes high performance DSSC.
Effect benefit of the present invention be utilize technology provided by the invention can make high efficiency, low cost to electrode and solar cell.With molybdenum carbide (Mo 2C), tungsten nitride (W 2N), molybdenum nitride (Mo 2N), vanadium carbide (VC), vanadium nitride (VN), niobium carbide (NbC), niobium nitride (NbN), tungsten carbide (WC, W 2C) as to electrode material, make paired electrode, make solar cell with light anode and electrolyte.
The present invention is because material therefor is cheap and simple to electrode and cell production process, solved that platinum electrode costs an arm and a leg and shortage of resources and utilize problem such as large-scale sputter.
Description of drawings
Accompanying drawing 1 is the schematic diagram of DSSC.
Accompanying drawing 2 is Ta Feier curves of electrode electro Chemical property detection.
Accompanying drawing 3 is ac impedance measurement curves of electrode.
Accompanying drawing 4 be with of the present invention to electrode and traditional platinum relatively to the performance of the DSSC of electrode preparation.Solid line and dotted line are respectively the current-voltage curve of the solar cell that molybdenum carbide makes electrode electrode and platinum.
Among Fig. 1: 1 photo-anode substrate; 2 conducting films; 3 semiconductive thin films; 4 dyestuffs; 5 electrolyte;
6 pairs of electrode base boards; 7 conducting films; 8 Catalytic Layer.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.The preparation method to electrode and solar cell of different materials involved in the present invention is identical, is that example illustrates with the molybdenum carbide at this.But therefore do not limit the invention among the scope of embodiments.
The preparation of embodiment 1 molybdenum carbide slurry
With molybdenum carbide fine powder 300mg, and titanium dioxide powder (P25, Degauss) 100mg, TritonX 100mg, after isopropyl alcohol 5mL and zirconium ancient unit of weight, equal to 1/24 liang 5g mixed, ball milling 4 hours was prepared into the spraying slurry, and organic solvent is removed in heating, then is prepared into printing and blade coating slurry.
Embodiment 2 spraying processes prepare the molybdenum carbide electrode
The slurry of making is uniformly sprayed on the FTO electro-conductive glass with airbrush, and spray distance is controlled at 10 centimetres, and spray pressure is controlled at 1000 Pascals.Under nitrogen protection, 500 ℃ were burnt electrode 30 minutes in tube furnace.
Embodiment 3 print processes prepare the molybdenum carbide electrode
With the slurry of preparation with screen printer print on the FTO electro-conductive glass, under nitrogen atmosphere, 500 ℃ were burnt electrode 30 minutes in tube furnace in Muffle furnace.
Embodiment 4 knife coatings prepare the molybdenum carbide electrode
With knife coating electrode slurry is coated on the FTO electro-conductive glass, under nitrogen atmosphere, 500 ℃ were burnt electrode 30 minutes in tube furnace in Muffle furnace.
Embodiment 5 knife coatings prepare platinum electrode
Using spraying process, is mass fraction that the aqueous isopropanol of 0.5% chloroplatinic acid is coated on the FTO electro-conductive glass uniformly, and under air atmosphere, 380 ℃ were burnt electrode 30 minutes in tube furnace in Muffle furnace.
Embodiment 6 electrode electro Chemical property detections (test of Ta Feier curve)
Work electrode is the molybdenum carbide electrode that embodiment 2 makes, and be the also molybdenum carbide electrode of embodiment 2 making to electrode, and electrolyte is the 0.1M lithium iodide, and 0.3M 1,2-dimethyl-3-propyl group-imidazoles iodine, the acetonitrile solution of 0.05M iodine and 0.5M tert .-butylpyridine.Sweep limits is from-1.0V to+1.0V, and sweep speed is 0.1V/s. for relatively, and we have done identical experiment with the platinum electrode of embodiment 5 making.With traditional platinum electrode is compared as can be seen from Ta Feier curve (Fig. 2), molybdenum carbide of the present invention has bigger exchange current density and limiting current density to electrode, illustrates that the molybdenum carbide electrode can effectively play catalytic action, promotes I 3 -Be reduced to I -
The test of embodiment 7 electrode AC impedances
Work electrode is the molybdenum carbide electrode that embodiment 2 makes, and to the molybdenum carbide electrode that electrode is also made of embodiment 2, electrolyte is with embodiment 6.Range of scanned frequencies from 100mHz to 1MHz, amplitude 10mV.Can see that from accompanying drawing 3 molybdenum carbide electrode of the present invention has littler interface resistance and load transfer resistance.
Application Example 1: preparation is based on the DSSC of molybdenum carbide to electrode
(1) making of light anode: on the FTO electro-conductive glass, titania slurry is prepared into TiO with knife coating 2Film, 500 ℃ of sintering 30 minutes are cooled to 80 ℃, soak 16 hours in ruthenium dye N719, are made into the light anode.
(2) the same embodiment of electrolyte
(3) to electrode be the molybdenum carbide electrode of 2 kinds of making of embodiment
(4) with the light anode of above-mentioned making, electrode is assembled,, injecting electrolyte, be assembled into the DSSC battery then at intermediate course with the encapsulation of sarin film.
Application Example 2: preparation is based on the DSSC of platinum to electrode
Electrode is changed the molybdenum carbide in the Application Example 1 into platinum to electrode, all the other manufacture methods are identical.
Application Example 3: the test of solar cell photoelectric conversion efficiency.
As shown in Figure 4, dotted line representative be an I-V curve to the DSSC of electrode with platinum, and it is I-V curve to the DSSC of electrode that solid line is represented with molybdenum carbide.As shown in Table 1, the open circuit voltage and the short circuit current of these two batteries are basic identical, and two efficiency of dye-sensitized solar battery also are more or less the same.This shows that molybdenum carbide is that a kind of very potential platinum electrode of costliness that can substitute is as the material of DSSC to electrode.
Table one: the parameter of DSSC
To electrode Open circuit voltage (mV) Short circuit current (mA/cm -2) Fill factor, curve factor (%) Conversion efficiency (%)
Platinum (Pt) ??821 ??12.80 ??64.5 ??6.77
Molybdenum carbide (Mo 2C) ??806 ??12.46 ??55.8 ??5.60

Claims (5)

1. a low cost that is used for DSSC is to electrode, it is characterized in that electrode material is the mixture of a kind of class alloy platinum material or more than one eka-platinium mixtures of material or class alloy platinum material and Pt, C electrode material.
2. a kind of low cost that is used for DSSC as claimed in claim 1 is characterized in that to electrode described class alloy platinum material is molybdenum carbide (Mo 2C), tungsten nitride (W 2N), molybdenum nitride (Mo 2N), vanadium carbide (VC), vanadium nitride (VN), niobium carbide (NbC), niobium nitride (NbN), tungsten carbide (WC, W 2C), its particle diameter is between 2nm-800 μ m.
3. a kind of low cost that is used for DSSC as claimed in claim 1 is characterized in that to electrode the following several method of eka-platinium material use is prepared: spraying process, knife coating, print process, chemical deposition, pyrolysismethod, galvanoplastic, sputtering method.
4. a kind of low cost that is used for DSSC as claimed in claim 1 is to electrode, it is characterized in that slurry to electrode is eka-platinium compound powder and inorganic compound adhesive to be dispersed in the organic solvent or the aqueous solution prepare.
5. a kind of low cost that is used for DSSC as claimed in claim 1 is characterized in that being used for DSSC to electrode.
CN 201010131086 2010-03-24 2010-03-24 Low-cost counter electrode for dye-sensitized solar battery Pending CN101770870A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010131086 CN101770870A (en) 2010-03-24 2010-03-24 Low-cost counter electrode for dye-sensitized solar battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010131086 CN101770870A (en) 2010-03-24 2010-03-24 Low-cost counter electrode for dye-sensitized solar battery

Publications (1)

Publication Number Publication Date
CN101770870A true CN101770870A (en) 2010-07-07

Family

ID=42503671

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010131086 Pending CN101770870A (en) 2010-03-24 2010-03-24 Low-cost counter electrode for dye-sensitized solar battery

Country Status (1)

Country Link
CN (1) CN101770870A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102176386A (en) * 2011-01-12 2011-09-07 南开大学 Dye sensitized solar battery counter electrode and manufacture method thereof
CN102522212A (en) * 2011-12-01 2012-06-27 河南大学 Counter electrode of dye-sensitized solar battery, preparation method and applications of tungsten disulfide and molybdenum disulfide
CN102543466A (en) * 2011-12-28 2012-07-04 大连理工大学 Counter electrode material for dye sensitization solar battery and preparation method and application thereof
CN102789906A (en) * 2012-05-28 2012-11-21 营口奥匹维特新能源科技有限公司 Preparation method for dye sensitized solar cell flexible Pt-carried counter electrode
WO2013075303A1 (en) * 2011-11-23 2013-05-30 海洋王照明科技股份有限公司 Active material for counter-electrode, method for preparing same, solar cell counter-electrode using active material for counter-electrode and preparation method thereof
CN103165289A (en) * 2011-12-14 2013-06-19 海洋王照明科技股份有限公司 Counter electrode of dye-sensitized solar battery, preparation method thereof, dye-sensitized solar battery and preparation method thereof
CN104715806A (en) * 2013-12-12 2015-06-17 三星电子株式会社 Electrically conductive thin films and electronic device comprising same
CN104916450A (en) * 2015-05-05 2015-09-16 苏州靖羽新材料有限公司 Capacitor plate material
CN109243829A (en) * 2018-09-19 2019-01-18 东莞理工学院 A kind of application of dye-sensitized cell electrode and preparation method thereof and MIL-47 material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006318770A (en) * 2005-05-13 2006-11-24 Japan Carlit Co Ltd:The Catalyst electrode of dye-sensitized solar battery, and dye-sensitized solar battery with same
CN101533720A (en) * 2009-04-10 2009-09-16 南开大学 Metal nitride electrode material for dye-sensitized solar cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006318770A (en) * 2005-05-13 2006-11-24 Japan Carlit Co Ltd:The Catalyst electrode of dye-sensitized solar battery, and dye-sensitized solar battery with same
CN101533720A (en) * 2009-04-10 2009-09-16 南开大学 Metal nitride electrode material for dye-sensitized solar cell

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102176386A (en) * 2011-01-12 2011-09-07 南开大学 Dye sensitized solar battery counter electrode and manufacture method thereof
WO2013075303A1 (en) * 2011-11-23 2013-05-30 海洋王照明科技股份有限公司 Active material for counter-electrode, method for preparing same, solar cell counter-electrode using active material for counter-electrode and preparation method thereof
CN102522212A (en) * 2011-12-01 2012-06-27 河南大学 Counter electrode of dye-sensitized solar battery, preparation method and applications of tungsten disulfide and molybdenum disulfide
CN102522212B (en) * 2011-12-01 2016-04-06 河南大学 A kind of DSSC is to the application of electrode, preparation method and tungsten disulfide and molybdenum bisuphide
CN103165289A (en) * 2011-12-14 2013-06-19 海洋王照明科技股份有限公司 Counter electrode of dye-sensitized solar battery, preparation method thereof, dye-sensitized solar battery and preparation method thereof
CN102543466A (en) * 2011-12-28 2012-07-04 大连理工大学 Counter electrode material for dye sensitization solar battery and preparation method and application thereof
CN102789906A (en) * 2012-05-28 2012-11-21 营口奥匹维特新能源科技有限公司 Preparation method for dye sensitized solar cell flexible Pt-carried counter electrode
CN104715806A (en) * 2013-12-12 2015-06-17 三星电子株式会社 Electrically conductive thin films and electronic device comprising same
US10099938B2 (en) 2013-12-12 2018-10-16 Samsung Electronics Co., Ltd. Electrically conductive thin films
CN104916450A (en) * 2015-05-05 2015-09-16 苏州靖羽新材料有限公司 Capacitor plate material
CN109243829A (en) * 2018-09-19 2019-01-18 东莞理工学院 A kind of application of dye-sensitized cell electrode and preparation method thereof and MIL-47 material
CN109243829B (en) * 2018-09-19 2021-04-13 东莞理工学院 Dye-sensitized cell electrode, preparation method thereof and application of MIL-47 material

Similar Documents

Publication Publication Date Title
CN101770870A (en) Low-cost counter electrode for dye-sensitized solar battery
Baglio et al. Influence of TiO2 film thickness on the electrochemical behaviour of dye-sensitized solar cells
Zhang et al. Increased power conversion efficiency of dye-sensitized solar cells with counter electrodes based on carbon materials
CN101388294B (en) Full carbon counter electrode dye-sensitized solar cell and preparing method
Wu et al. TiC/Pt composite catalyst as counter electrode for dye-sensitized solar cells with long-term stability and high efficiency
KR20080006735A (en) Photovoltaic cell using catalyst supporting carbon nanotube and method for producing the same
CN101901693A (en) Graphene composite dye-sensitized solar cell light anode and preparation method thereof
CN101620939B (en) Semiconductor electrode, preparation method thereof and solar cell comprising semiconductor electrode
CN101188257B (en) Carbon plasma for electrode of dye sensitization solar battery pair and its making method
CN107833752B (en) It is a kind of for dye-sensitized solar cells to the material and preparation method thereof of electrode
Sedghi Effect of multi walled carbon nanotubes as counter electrode on dye sensitized solar cells
CN101567268A (en) Method for preparing ternary two-layer titanium dioxide film
CN101022136A (en) Alkaline-earth metal salt decorative nano crystal semiconductor optical anode, producing method and application thereof
CN108364792A (en) A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material
CN103021509B (en) DSSC is to electrode carbon pastes
US20100300537A1 (en) Dye-sensitized solar cell and organic solvent-free electrolyte for dye-sensitized solar cell
CN101620938B (en) Semiconductor electrode, preparation method thereof and solar cell comprising semiconductor electrode
CN102280256B (en) Dye-sensitized solar cell quasi solid electrolyte and method for preparing solar cell by using same
CN104538191B (en) The preparation method and dye-sensitized solar cell anode and DSSC of dye-sensitized solar cell anode
CN103887071A (en) Flexible nano paper-base compound photo-anode for dye-sensitized solar cell and preparation method thereof
CN110085428A (en) A kind of compound light anode of titanium dioxide/graphene and preparation method thereof
Cao et al. Electrocatalytically active MoSe2 counter electrode prepared in situ by magnetron sputtering for a dye-sensitized solar cell
CN101572189A (en) Semiconductor electrode for dye-sensitized solar cells, preparation method thereof and cell
Zhao et al. Screen-printed Pt counter electrodes exhibiting high catalytic activity
TWI407579B (en) Method for fabricating electrode structures on substrate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20100707