CN203377110U - A dye-sensitized solar cell composite-structure counter electrode - Google Patents

A dye-sensitized solar cell composite-structure counter electrode Download PDF

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CN203377110U
CN203377110U CN201320430262.2U CN201320430262U CN203377110U CN 203377110 U CN203377110 U CN 203377110U CN 201320430262 U CN201320430262 U CN 201320430262U CN 203377110 U CN203377110 U CN 203377110U
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electrode
dssc
fto
counter electrode
composite construction
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云斯宁
杜婷婷
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Xian University of Architecture and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The utility model discloses a dye-sensitized solar cell composite-structure counter electrode. The composite-structure counter electrode comprises a FTO or ITO substrate, and a counter electrode catalyst layer disposed on the FTO or ITO substrate. The FTO or ITO substrate comprises a glass substrate and a FTO or ITO conductive film layer disposed on the glass substrate. The counter electrode catalyst layer is a composite layer formed by a transition metal binary or ternary compound and a carbon material or conductive polymer. The composite-structure counter electrode has excellent electrochemical, catalytic and electrochemical stability performance, and may substitute for precious metal Pt electrode to be used in dye-sensitized solar cell device. It has low cost and easy manipulation to construct counter electrode catalytic material and counter electrode thin films. The composite-structure counter electrode is strongly compatible with photo-anode preparation technology and has application and popularization value.

Description

A kind of DSSC composite construction is to electrode
Technical field
The utility model belongs to green renewable and clean energy resource technical field, is specifically related to a kind of DSSC composite construction to electrode.
Background technology
It is the ultimate challenge that human society faces that energy shortage and fossil fuel are used the environmental pollution brought.The development and utilization of regenerative resource (solar energy, wind energy, biomass energy etc.) is the key point addressed this problem.The regenerative resource that solar energy is the abundantest as resource, the advantage that it is unique and huge exploitation potential make the development and utilization of solar cell become very important in recent years research topic.
Compare Switzerland scientist M. in 1991 with thin-film solar cells with silica-based
Figure BDA00003533592000011
the DSSC of new generation of utility model (dye sensitized solar cell, DSSC), because its cost of manufacture is low, simple, the abundant raw material of technique, environmental protection, theoretical energy conversion efficiency be high, be convenient to large-area manufacturing, lightweight, the characteristics such as colorful, pliable and tough, transparent, have more business development and be worth, become emphasis and the focus of research in world wide.
Traditional DSSC is mainly by nanocrystalline TiO 2the light anode, to formations such as electrode catalyst, sensitizing dyestuff and electrolyte.Main Function to electrode catalyst is: 1. as electronic receiver, from external circuit, collect electronics; 2. as efficient catalyst, the iodide ion in reduction electrolyte, promote the regeneration of sensitizing dyestuff molecule.As one of most important building block of DSSC---to electrode catalyst, take the precious metals pt electrode as main.But the use of precious metals pt electrode catalyst in DSSC is faced with formidable challenges.Main manifestations is: (1) precious metals pt price is high; (2) precious metals pt is rare at occurring in nature, reserves are limited; (3) precious metals pt is worldwide supplied with limited; (4) precious metals pt easily is corroded in to electrolytical DSSC containing the iodine electricity.In addition, along with Pt catalyst or the eelctro-catalyst wilderness demand in fields such as chemistry and fine chemistry industry, fuel cell, organic matter degradation, electrolysis, photoelectrochemical cell, pollution controls, the replacement precious metals pt of developing green environmental protection, cheap, excellent performance is to electrode material, meet to the Pt metal demand at different catalytic fields, become the major impetus of electrocatalysis material research and development.
In recent years, different research institutions mainly concentrates on the research and development of electrode catalytic materials DSSC both at home and abroad: 1. non-Pt is to electrode catalytic materials (as material with carbon element, conducting polymer etc.); 2. class Pt is to electrode catalytic materials (as oxide, carbide, nitride, sulfide, phosphide, selenides etc.); 3. combined counter electrode catalysis material.The subject matter of material with carbon element is poor with the caking property of conductive substrates.Too thin to electrode film, the catalytic activity deficiency; Too thick to electrode film, not only device volume heaviness, and conducting film easily comes off from conductive substrates, affects the stability of battery.In addition, material with carbon element, for transparent, translucent, colorful DSSC, is not desirable to electrode material.The poor heat stability of conducting polymer materials, resistance to corrosion is poor.For the most of class Pt that developed, to electrode catalytic materials, electricity conversion is all more on the low side, and repeatability and stability are not good enough, has hindered this class catalysis material further applying in chemistry and electrochemical field.
By contrast, the combined counter electrode catalysis material can take full advantage of the cooperative effect formed between the composite materials each component, makes the performance of electrode catalyst and the performance of battery are greatly improved, and has guaranteed the stable, reliable and practical of electrode catalyst performance.
Therefore, the alternative Pt electrode (composite construction is to electrode) of exploitation high-performance, high efficiency, low cost, long-time stability, be the important channel that promotes the DSSC industrialization process.
The utility model content
The purpose of this utility model is to overcome the existing shortcoming and defect to electrode, provides a kind of composite construction of alternative Pt metal to electrode.This is to the electrode abundant raw materials, and cost of manufacture is low, and strong with preparation technology's compatibility of light anode, has good electrochemistry, catalysis and electrochemical stability performance, can replace the precious metals pt application of electrode in the DSSC device.
In order to achieve the above object, the utility model adopts following technical proposals to realize:
A kind of DSSC composite construction is to electrode, this composite construction comprises FTO or ITO substrate to electrode, and be arranged on FTO or ITO substrate to pole catalyze layer, described FTO or ITO substrate comprise glass substrate, and are arranged on FTO or ITO conductive film layer on glass substrate; The described composite bed that is transition metal binary or ternary compound layer and material with carbon element or conductive polymer coating composition to pole catalyze layer.
Further, described transition metal binary or ternary compound layer consist of electrode catalytic materials oxide, carbide, nitride, sulfide, phosphide, selenides, nitrogen oxide or the carbonitride of transition metal Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sc, Y, Fe, Co, Ni, Mn, Cu, Zn.
Further, described material with carbon element is activated carbon, carbon black, acetylene black, conductive carbon, graphite, pigment carbon, carbon fiber, carbon nano-tube, C60, C70 or Graphene.
Further, described conducting polymer is poly-3,4-ethylene dioxythiophene (PEDOT), polystyrene sodium sulfate salt (PSS), polythiofuran derivative (PProDOT, PProDOT-Et 2), polypyrrole (PPy) or aniline (ANI).
Further, described its lamination layer structure of pole catalyze layer is consisted of electrode catalytic materials composite construction, lamination layer structure is meso-hole structure to electrode catalytic materials, and aperture is 3～10nm, and specific area is 300～1000m 2/ g.
Further, the described thickness to pole catalyze layer is 10～30 μ m.
Further, the thickness of described material with carbon element or conductive polymer coating is 5～10 μ m.
The technique effect that the utility model brings is:
The composite construction of the alternative precious metals pt electrode that the first, the utility model provides to electrode catalytic materials as DSSC to electrode, the prices of raw and semifnished materials are cheap, manufacture craft is simple, and under identical experiment condition, its photovoltaic performance can be complementary with the precious metals pt electrode.
The composite construction of the alternative precious metals pt electrode that the second, the utility model provides, to electrode, can effectively solve the predicament that precious metals pt faces, and as high as price, shortage of resources, matching are poor etc.On the basis of retainer member high light electric energy conversion efficiency (PCE) and electrochemical stability, can decrease DSSC to the cost of electrode, the commercialization that helps lend some impetus to DSSC is applied.
The composite construction of the alternative precious metals pt electrode that three, the utility model provides is to electrode, take full advantage of the cooperative effect that forms the compound each component, make composite construction be better than the performance of single structure to electrode to the performance of electrode, show more outstanding photovoltaic performance.In addition, this compound is high to electrode electro Chemical stability, and practical value is large.
The composite construction of the alternative precious metals pt electrode that four, the utility model provides is to electrode, its meso-hole structure is conducive to transmission and the collection of electronics, facilitate the transmission of reactant molecule, for the reduction of ion provides more catalytic site, be conducive to the regeneration of dye molecule and improving of catalytic activity.
The composite construction of the alternative precious metals pt electrode that five, the utility model provides is to electrode, and its good catalytic performance is expected to be applied to the fields such as fuel cell, biology sensor, hydrogen manufacturing, energy storage, organic matter degradation and pollution control.
The accompanying drawing explanation
Fig. 1 is the utility model structural representation;
Fig. 2 is the battery device schematic diagram (circle is depicted as DSSC to pole catalyze layer) with the utility model structure construction;
Fig. 3 is the SEM figure (tantalum oxide (white) inlay mesoporous carbon) of the utility model to electrode structure;
Fig. 4 is the SEM figure (ramet (white) inlay mesoporous carbon) of the utility model to electrode structure;
Fig. 5 is for adopting the photovoltaic property curve of embodiment 1～2 and 3～6 pairs of create electrode DSSC devices of Comparative Examples.
In figure: 100, to electrode; 101, glass substrate; 201, upper glass substrate; 102, FTO or ITO conductive film layer; 202, upper FTO or ITO conductive film layer; 103, material with carbon element or conductive polymer coating; 104, transition metal binary or ternary compound layer; 105, FTO or ITO substrate; 106, to pole catalyze layer; 200, light anode; 203, the TiO of dye sensitization 2layer; 204, the TiO of light scattering 2layer; 301, electrolyte layer; 401, encapsulating film; 111, incident light.
Embodiment
In order to describe technology contents of the present utility model and feature in detail, below in conjunction with embodiment and be equipped with accompanying drawing the utility model is further described.
As shown in Figure 1, the utility model is that a kind of DSSC composite construction is to electrode, this composite construction comprises FTO or ITO substrate 105 to electrode 100, and be arranged on FTO or ITO substrate 105 to pole catalyze layer 106, FTO or ITO substrate 105 comprise glass substrate 101, and are arranged on FTO or ITO conductive film layer 102 on glass substrate 101; The described composite bed that is transition metal binary or ternary compound layer 104 and material with carbon element or conductive polymer coating 103 compositions to pole catalyze layer 106.
Wherein, transition metal binary or ternary compound layer 104 consist of electrode catalytic materials oxide, carbide, nitride, sulfide, phosphide, selenides, nitrogen oxide or the carbonitride of early stage transition metal Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sc, Y, Fe, Co, Ni, Mn, Cu, Zn etc.Material with carbon element or conductive polymer coating 103 consist of electrode catalytic materials material with carbon element or conducting polymer; Material with carbon element is activated carbon, carbon black, acetylene black, conductive carbon, graphite, pigment carbon, carbon fiber, carbon nano-tube, C60, C70 or Graphene; Conducting polymer is poly-3,4-ethylene dioxythiophene (PEDOT), polystyrene sodium sulfate salt (PSS), polythiofuran derivative (PProDOT, PProDOT-Et 2), polypyrrole (PPy) or aniline (ANI).
This consists of electrode catalytic materials composite construction pole catalyze layer 106 its lamination layer structures electrode structure, and lamination layer structure is meso-hole structure to electrode catalytic materials, and aperture is 3～10nm, and specific area is 300～1000m 2/ g.
And the thickness to pole catalyze layer 106 of the present utility model is 10～30 μ m, the thickness of material with carbon element or conductive polymer coating 103 is 5～10 μ m.
Fig. 2 has provided and has utilized the DSSC battery structure of the utility model composite construction to create electrode, and battery comprises electrode 100, light anode 200, electrolyte layer 301 and encapsulating film 401; Electrode 100 is comprised to FTO or ITO substrate 105(glass substrate 101 and FTO or ITO conductive film layer 102 on it), and be arranged on FTO or ITO substrate 105 to pole catalyze layer 106(material with carbon element or conductive polymer coating 103 and transition metal binary or ternary compound layer 104); Light anode 200 comprises upper glass substrate 201 and is arranged on upper FTO or the ITO conductive film layer 202 of upper glass substrate 201 inboards, be provided with successively the TiO of dye sensitization below upper FTO or ITO conductive film layer 202 2the TiO of layer 203 and light scattering 2layer 204; TiO in the dye sensitization to pole catalyze layer 106, light anode 200 to electrode 100 2the TiO of layer 203 and light scattering 2the periphery of layer 204 is provided with encapsulating film 401, will be packaged together to electrode 100, light anode 200 and electrolyte layer 301; Conductive film layer 102 is connected with load by extraction electrode with conductive film layer 202; Incident light 111 is from 201 incidents of upper strata glass substrate.
Adopt the utility model composite construction to two kinds in electrode 100(transition metal, as tantalum oxide is inlayed mesoporous carbon (Fig. 3), ramet is inlayed mesoporous carbon (Fig. 4) electrode catalyst is formed, meso-hole structure, aperture is 3～10nm, specific area is 300～1000m 2/ g), the mesoporous TiO of light anode 200(N719 dye sensitization 2(P25, Degussa, Germany) nanoparticle film), use and contain the iodide ion electricity to (I 3 -/ I -) electrolyte 301(0.6M iodate-1-butyl-3-methylimidazole, 0.06M lithium iodide, 0.03M iodine, 0.5M4-tert .-butylpyridine, 0.1M guanidinium isothiocyanate, solvent is acetonitrile) and encapsulating film 401, according to standard method, this is become to the DSSC battery (M. of standard to electrode assembling the structural representation of utility model DSSC device is as shown in the Fig. 2 of institute), cell active area 0.16cm 2, carry out packaging and testing under AM1.5 simulated solar irradiation reference condition, its photovoltaic performance parameter is as shown in table 1, and its voltage-current characteristic curve is as shown in Figure 5.
Table 1 the utility model different materials forms photovoltaic device photoelectric properties parameter comparison
Figure BDA00003533592000072
Annotate: the listed photoelectric properties parameter of table 1 is the selected embodiment of the utility model structure.In addition, table performance parameter is not the optimum value that the photovoltaic device test obtains, but multiple batches of repeated experiments is measured the metastable empirical value obtained.
By more known (embodiment in table 1 and Comparative Examples), the composite construction of alternative precious metals pt electrode to electrode (for example, tantalum oxide is inlayed mesoporous carbon, ramet is inlayed mesoporous carbon), take full advantage of the cooperative effect (electrocatalysis characteristic that oxide and carbide are good that forms the compound each component; The catalytic performance that mesoporous carbon is outstanding and outstanding electronics, ionic conduction performance), make composite construction (tantalum oxide is inlayed mesoporous carbon, ramet is inlayed mesoporous carbon) be better than single structure (oxide, carbide and mesoporous carbon) to the performance of electrode to the performance of electrode, show more outstanding photovoltaic performance.In addition, this compound is high to electrode electro Chemical stability, and practical value is large.
The utility model composite construction is to electrode, be that transition metal binary or ternary compound are inlayed or decorate material with carbon element or conducting polymer, there is good chemical property, catalytic performance and electrochemical stability, can replace the precious metals pt application of electrode in the DSSC device.In addition, to electrode catalytic materials with to the structure of electrode film, the cost of raw material is cheap, and technological operation is simple, and strong with preparation technology's compatibility of light anode.Utilize this structure, can take full advantage of the cooperative effect formed between the composite materials each component, make the performance of electrode catalyst and the performance of battery are greatly improved, guaranteed the stable, reliable and practical of electrode catalyst performance.
The above, be only the embodiment of the utility model for the utility model application, can make those skilled in the art more fully understand the utility model, but not the utility model be done to any restriction.Every scope given according to technical solutions of the utility model and to any simple modification made for any of the above embodiments, change and equivalent structure transformation, all belong to the protection range of technical solutions of the utility model.

Claims (7)

1. a DSSC composite construction is to electrode, this composite construction comprises FTO or ITO substrate (105) to electrode, and be arranged on FTO or ITO substrate (105) to pole catalyze layer (106), it is characterized in that: described FTO or ITO substrate (105) comprise glass substrate (101), and are arranged on FTO or ITO conductive film layer (102) on glass substrate (101); The described composite bed that is transition metal binary or ternary compound layer (104) and material with carbon element or conductive polymer coating (103) composition to pole catalyze layer (106).
2. a kind of DSSC composite construction according to claim 1 is to electrode, it is characterized in that, described transition metal binary or ternary compound layer (104) consist of electrode catalytic materials oxide, carbide, nitride, sulfide, phosphide, selenides, nitrogen oxide or the carbonitride of transition metal Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sc, Y, Fe, Co, Ni, Mn, Cu, Zn.
3. a kind of DSSC composite construction according to claim 1 is to electrode, it is characterized in that, in described material with carbon element or conductive polymer coating (103), material with carbon element is activated carbon, carbon black, acetylene black, conductive carbon, graphite, pigment carbon, carbon fiber, carbon nano-tube, C60, C70 or Graphene.
4. a kind of DSSC composite construction according to claim 1 is to electrode, it is characterized in that, in described material with carbon element or conductive polymer coating (103), conducting polymer is poly-3,4-ethylenedioxy thiophene (PEDOT), polystyrene sodium sulfate salt (PSS), polythiofuran derivative (PProDOT, PProDOT-Et 2), polypyrrole (PPy) or aniline (ANI).
5. a kind of DSSC composite construction according to claim 1 is to electrode, it is characterized in that, described to its lamination layer structure of pole catalyze layer (106) by electrode catalytic materials is formed, lamination layer structure is meso-hole structure to electrode catalytic materials, aperture is 3～10nm, and specific area is 300～1000m 2/ g.
6. a kind of DSSC composite construction according to claim 1, to electrode, is characterized in that, the described thickness to pole catalyze layer (106) is 10～30 μ m.
7. a kind of DSSC composite construction according to claim 1, to electrode, is characterized in that, the thickness of described material with carbon element or conductive polymer coating (103) is 5～10 μ m.
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Cited By (9)

* Cited by examiner, † Cited by third party
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CN103971937A (en) * 2014-05-06 2014-08-06 吉林大学 Dye-sensitized solar cell composite pair electrode and preparing method thereof
CN104465116A (en) * 2014-12-30 2015-03-25 中国科学院上海硅酸盐研究所 Counter electrode of dye-sensitized solar cell and preparation method of counter electrode
CN104810158A (en) * 2015-04-29 2015-07-29 河北大学 Counter electrode material of sensitized solar battery and manufacturing method of counter electrode material
CN105513809A (en) * 2016-01-11 2016-04-20 上海交通大学 Copper cobalt germanium sulphur nanocrystalline, copper cadmium cobalt sulphur counter electrode, and preparation methods and application of copper cobalt germanium sulphur nanocrystalline and copper cobalt germanium sulphur counter electrode
CN106090804A (en) * 2016-07-27 2016-11-09 杨炳 A kind of outdoor illumination device possessing spontaneous electrical function
CN106920695A (en) * 2016-12-31 2017-07-04 武汉理工大学 Copper-cladding Aluminum Bar iron carbide powder powder material and its application
CN107742582A (en) * 2017-10-24 2018-02-27 苏州妙文信息科技有限公司 A kind of electrode of solar battery material and its preparation
CN108492994A (en) * 2018-03-22 2018-09-04 福州大学 A kind of preparation method of vulcanization witch culture conductive polythiophene for dye-sensitized solar cells to electrode
CN115172058A (en) * 2022-08-01 2022-10-11 河南大学 MoP/MoNiP 2 Composite material, preparation method and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103971937B (en) * 2014-05-06 2016-09-07 吉林大学 A kind of dye-sensitized solar cells combined counter electrode and preparation method thereof
CN103971937A (en) * 2014-05-06 2014-08-06 吉林大学 Dye-sensitized solar cell composite pair electrode and preparing method thereof
CN104465116A (en) * 2014-12-30 2015-03-25 中国科学院上海硅酸盐研究所 Counter electrode of dye-sensitized solar cell and preparation method of counter electrode
CN104810158B (en) * 2015-04-29 2018-02-06 河北大学 A kind of sensitization solar battery is to electrode material and preparation method thereof
CN104810158A (en) * 2015-04-29 2015-07-29 河北大学 Counter electrode material of sensitized solar battery and manufacturing method of counter electrode material
CN105513809A (en) * 2016-01-11 2016-04-20 上海交通大学 Copper cobalt germanium sulphur nanocrystalline, copper cadmium cobalt sulphur counter electrode, and preparation methods and application of copper cobalt germanium sulphur nanocrystalline and copper cobalt germanium sulphur counter electrode
CN106090804A (en) * 2016-07-27 2016-11-09 杨炳 A kind of outdoor illumination device possessing spontaneous electrical function
CN106920695A (en) * 2016-12-31 2017-07-04 武汉理工大学 Copper-cladding Aluminum Bar iron carbide powder powder material and its application
CN106920695B (en) * 2016-12-31 2018-07-17 武汉理工大学 Copper-cladding Aluminum Bar iron carbide powder powder material and its application
CN107742582A (en) * 2017-10-24 2018-02-27 苏州妙文信息科技有限公司 A kind of electrode of solar battery material and its preparation
CN108492994A (en) * 2018-03-22 2018-09-04 福州大学 A kind of preparation method of vulcanization witch culture conductive polythiophene for dye-sensitized solar cells to electrode
CN108492994B (en) * 2018-03-22 2019-10-15 福州大学 It is a kind of to vulcanize witch culture conductive polythiophene to the preparation method of electrode for dye-sensitized solar cells
CN115172058A (en) * 2022-08-01 2022-10-11 河南大学 MoP/MoNiP 2 Composite material, preparation method and application thereof
CN115172058B (en) * 2022-08-01 2023-10-10 河南大学 MoP/MoNiP 2 Composite material, preparation method and application thereof

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