CN102751098A - Photoanode of dye-sensitized solar cell - Google Patents

Photoanode of dye-sensitized solar cell Download PDF

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Publication number
CN102751098A
CN102751098A CN2012102162444A CN201210216244A CN102751098A CN 102751098 A CN102751098 A CN 102751098A CN 2012102162444 A CN2012102162444 A CN 2012102162444A CN 201210216244 A CN201210216244 A CN 201210216244A CN 102751098 A CN102751098 A CN 102751098A
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graphene
photoanode
inorganic nanoparticles
solar cell
dye
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CN102751098B (en
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徐征
赵谡玲
徐叙瑢
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Beijing Jiaotong University
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Beijing Jiaotong University
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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
    • 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
    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses a photoanode of a dye-sensitized solar cell, which belongs to the technical field of the preparation of electrode materials. The photoanode is formed by the method that inorganic nanoparticles, manganese dioxide nano material and graphene are evenly mixed and applied on the surface of substrate material, wherein the inorganic nanoparticles, the manganese dioxide nano material and the graphene respectively account for 40-83%, 15-20% and 2-40% of the total mass. The photoanode disclosed by the invention has good electrical conductivity, thermal conductivity and mechanical property, and gives an optimum range for the mixing ratio of the inorganic nanoparticles, the manganese dioxide nano material and the graphene. The photoanode with optimum performance can be obtained within the number range provided by the invention, and therefore a dye-sensitized solar cell with higher photoelectric conversion efficiency can be obtained under the same experiment condition.

Description

A kind of light anode of DSSC
Technical field
The present invention relates to a kind of light anode that is used for DSSC, belong to the electrode material preparing technical field.
Background technology
Society is in high speed development, and the mankind are being faced with unprecedented energy crisis and environmental pollution, the utilization of regenerative resource are become the only way of human kind sustainable development.Solar cell is as pollution-free clean energy resource equipment, and its development receives the great attention of countries in the world government.Extensive use at present mainly be silica-based solar cell, but its price is very expensive.DSSC has that cost is low, stability height, environmental friendliness, can be prepared into advantage such as flexible battery, is the novel solar battery that is hopeful alternative traditional silicon based photovoltaic cells most.
The method of traditional preparation process DSSC light anode is at nano-TiO 2Add surfactant in the particle, then through silk screen printing, direct method depositing nano TiO on conductive substrates such as film 2Membrana granulosa obtains DSSC light anode through high-temperature heat treatment.The light anode major defect of this method preparation is that porosity is relatively low, and specific area is not high enough, and owing to the undesirable electron diffusion coefficient that causes of contact between particle is less, thereby hinder the raising of DSSC cell photoelectric conversion efficiency.Given this, explore the light anode that new method prepares bigger serface and homogeneous pore-size distribution the conversion efficiency that improves DSSC is had meaning greatly.
Graphene is a kind of new material by carbon atom tightly packed one-tenth hexagonal lattice structure on two-dimensional space.Graphene is to constitute zero-bit fullerene, one dimension CNT, the basic structural unit of sp2 hydridization carbon such as said three-dimensional body phase graphite.Graphene is a kind of material that does not have energy gap, shows metallicity; The Graphene of individual layer, each carbon atom all have the not electronics of Cheng Jian, therefore have extraordinary conductivity.Because mechanical performance and physical property that Graphene is excellent become one of research focus of material science.Graphene has very large specific area and excellent conducting performance is good electrode material.
In recent years, the electrode that different types of electrode material makes after mixing has obtained extensive studies.Especially after Graphene and metal oxide mixed according to a certain percentage, the combination electrode of making had obtained paying close attention to widely especially.Find that in the process of research group's bunch phenomenon takes place Graphene easily, mixes inhomogeneously, can not make full use of the performance of the excellence of Graphene, cause the not significantly raising of performance of this combination electrode.
Summary of the invention
The object of the invention provides a kind of preparation method with dye-sensitized solar cell anode of good electrochemical, and the production cost of this solar battery light anode is low, and the preparation method is simple; Low price; Characteristics such as light weight has the solution handlability, and processing and forming is good.
The present invention realizes through following technical proposals:
A kind of light anode of DSSC; Described smooth anode is evenly mixed by inorganic nanoparticles, nano material of manganese dioxide and Graphene and is coated in substrate material surface, and wherein inorganic nanoparticles, nano material of manganese dioxide and the Graphene mass percent that accounts for gross mass is respectively 40%-83%, 15%-20%, 2%-40%.
A kind of preparation method of dye-sensitized solar cell anode; It is characterized in that: with Graphene nanostructure, bigger serface is raw material; Mix with inorganic nanoparticles, nano material of manganese dioxide; Be coated in substrate material surface, the preparation dye-sensitized solar cell anode, the preparation method comprises the steps:
The first step: will have in the water-soluble or organic solvent of water miscible single or multiple lift Graphene, ultrasonic Treatment is dissolved to it fully; The concentration range of Graphene solution is between 10.5-28mg/ml;
Second step: the Graphene solution that inorganic nanoparticles, nano material of manganese dioxide and the first step are obtained mixes and carries out ultrasonic dispersion; Obtain composite material, wherein inorganic nanoparticles, nano material of manganese dioxide and the Graphene mass percent that accounts for gross mass is respectively 40%-83%, 15%-20%, 2%-40%;
The 3rd step: second step was obtained more than the normal temperature held 48h, drying the laminated film that the back obtains the single or multiple lift Graphene on the surface that composite material is prepared into base material; Said base material is transparent conducting glass, metallic substrates, material with carbon element substrate or polyethylene, polystyrene and polyester macromolecule substrate;
The 4th step: the 3rd step was prepared into the laminated film of the single or multiple lift Graphene that substrate material surface obtains, reduces, obtain light anode based on the single or multiple lift Graphene through reducing agent; Or under the protection of nitrogen or argon gas, after 650-800 ℃ of roasting, obtain light anode based on the single or multiple lift Graphene.
Preferably, said have water miscible single or multiple lift Graphene through graphite chemical oxidation method or the acquisition of graphite organic functional method.
Preferably, said inorganic nanoparticles is TiO 2, ZnO, SnO 2, Nb 2O 5, Al 2O 3, In 2O 3, CuO, NiO, MgO, SiO 2In one or more oxide.
Preferably, the lip-deep method that is prepared into base material in said the 3rd step comprises immersion, spin coating or spraying.
Preferably, said reducing agent is pure hydrazine solution, hydrazine steam, hydrazine hydrate steam or sodium borohydride.
Preferably, said organic solvent is acetone or N, dinethylformamide DMF.
Beneficial effect of the present invention:
The present invention is being that graphite is raw material; Prepare water miscible single or multiple lift Graphene through chemical method; Method through organic functional then; Prepare organic soluble single or multiple lift Graphene, the mixture that will be mixed with inorganic nanoparticles, nano material of manganese dioxide and Graphene solution through the method that applies is prepared into moulding on the surface of base material, after electronation or roasting can obtain the light anode based on the single or multiple lift Graphene.The light anode of this preparation method's preparation has good conductivity, also have good thermal conductivity and mechanical property simultaneously, and its production cost is very low; The preparation method is simple, low price, light weight; Has the solution handlability; Processing and forming is good, does not need large complicated instrument, can prepare the sample of various sizes and shape.In addition; Mixed proportion for inorganic nanoparticles, nano material of manganese dioxide and Graphene has provided best scope; Can access the light anode of optimum performance in the number range of the present invention's proposition; Particularly the nano material of manganese dioxide percentage 15%-20% that accounts for gross mass has played crucial effect, and the percentage that accounts for gross mass surpasses 20% or be lower than at 15% o'clock, and the photoelectric conversion efficiency of the DSSC of preparation obviously descends.
Description of drawings
Fig. 1 is the structural representation of DSSC.
Fig. 2 is for adopting the SEM photo of dye-sensitized solar cell anode of the present invention.
Embodiment
Embodiment 1
Will be soluble in water through the multi-layer graphene that the graphite chemical oxidation method obtains, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 10.5mg/ml.With ZnO nano particle, MnO 2Nano material and Graphene solution are according to ZnO nano particle, MnO 2The mass percent of nano material and Graphene is respectively 40%, 20%, 40% and mixes, and carries out ultrasonic dispersion.The composite material that obtains is spun on the surface of polyester macromolecule substrate, normal temperature held 48h dries the laminated film that the back obtains multi-layer graphene.Laminated film with the multi-layer graphene that is spun to the acquisition of polyester macromolecule substrate surface reduces through pure hydrazine solution, obtains the complex light anode based on multi-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 7.23% with N719.
Embodiment 2
To be dissolved in the acetone through the single-layer graphene that graphite organic functional method obtains, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 28mg/ml.With Nb 2O 5Nano particle, MnO 2Nano material and Graphene solution are according to Nb 2O 5Nano particle, MnO 2The mass percent of nano material and Graphene is respectively 83%, 15%, 2% and mixes, and carries out ultrasonic dispersion.The composite material that obtains is sprayed on the surface of metallic substrates, normal temperature held 60h dries the laminated film that the back obtains single-layer graphene.With the laminated film of the single-layer graphene that sprays to the acquisition of metallic substrates substrate surface, under the protection of nitrogen or argon gas, after 650 ℃ of roastings, obtain complex light anode based on single-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 7.28% with N719.
Embodiment 3
To be dissolved in N through the multi-layer graphene that graphite organic functional method obtains, among the dinethylformamide DMF, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 20mg/ml.With Al 2O 3Nano particle, MnO 2Nano material and Graphene solution are according to Al 2O 3Nano particle, MnO 2The mass percent of nano material and Graphene is respectively 70%, 18%, 12% and mixes, and carries out ultrasonic dispersion.The composite material that obtains is sprayed on the surface of transparent conducting glass substrate, normal temperature held 72h dries the laminated film that the back obtains multi-layer graphene.The laminated film of the multi-layer graphene that the surface that sprays to the transparent conducting glass substrate is obtained under the protection of nitrogen or argon gas, after 800 ℃ of roastings, obtains the complex light anode based on multi-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 7.45% with N719.
Comparative Examples 1
Will be soluble in water through the multi-layer graphene that the graphite chemical oxidation method obtains, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 10.5mg/ml.Is that 1:1 mixes with ZnO nano particle and Graphene solution according to the mass percent of ZnO nano particle and Graphene, and carries out ultrasonic dispersion.The composite material that obtains is spun on the surface of polyester macromolecule substrate, normal temperature held 48h dries the laminated film that the back obtains multi-layer graphene.Laminated film with the multi-layer graphene that is spun to the acquisition of polyester macromolecule substrate surface reduces through pure hydrazine solution, obtains the complex light anode based on multi-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 6.18% with N719.
Comparative Examples 2
To be dissolved in the acetone through the single-layer graphene that graphite organic functional method obtains, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 28mg/ml.With Nb 2O 5Nano particle, MnO 2Nano material and Graphene solution are according to Nb 2O 5Nano particle, MnO 2The mass percent of nano material and Graphene is respectively 83%, 10%, 7% and mixes, and carries out ultrasonic dispersion.The composite material that obtains is sprayed on the surface of metallic substrates, normal temperature held 60h dries the laminated film that the back obtains single-layer graphene.With the laminated film of the single-layer graphene that sprays to the metal substrate surface acquisition, under the protection of nitrogen or argon gas, after 650 ℃ of roastings, obtain complex light anode based on single-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 5.32% with N719.
Comparative Examples 3
To be dissolved in N through the multi-layer graphene that graphite organic functional method obtains, among the dinethylformamide DMF, ultrasonic Treatment is dissolved to it fully, and the concentration of Graphene solution is 20mg/ml.With Al 2O 3Nano particle, MnO 2Nano material and Graphene solution are according to Al 2O 3Nano particle, MnO 2The mass percent of nano material and Graphene is respectively 70%, 25%, 5% and mixes, and carries out ultrasonic dispersion.The composite material that obtains is sprayed on the surface of transparent conducting glass substrate, normal temperature held 72h dries the laminated film that the back obtains multi-layer graphene.The laminated film of the multi-layer graphene that the surface that sprays to the transparent conducting glass substrate is obtained under the protection of nitrogen or argon gas, after 800 ℃ of roastings, obtains the complex light anode based on multi-layer graphene.Adopting above-mentioned complex light anode, is that the photoelectric conversion efficiency of dye-sensitized solar cell prepared reaches 5.81% with N719.

Claims (3)

1. the light anode of a DSSC; It is characterized in that: described smooth anode is evenly mixed by inorganic nanoparticles, nano material of manganese dioxide and Graphene and is coated in substrate material surface, and wherein inorganic nanoparticles, nano material of manganese dioxide and the Graphene mass percent that accounts for gross mass is respectively 40%-83%, 15%-20%, 2%-40%.
2. the light anode of DSSC according to claim 1, it is characterized in that: said inorganic nanoparticles is TiO 2, ZnO, SnO 2, Nb 2O 5, Al 2O 3, In 2O 3, CuO, NiO, MgO, SiO 2In one or more oxide.
3. the light anode of DSSC according to claim 1, it is characterized in that: said base material is transparent conducting glass substrate, metallic substrates, material with carbon element substrate, polyethylene, polystyrene or polyester macromolecule substrate.
CN201210216244.4A 2012-06-26 2012-06-26 A kind of light anode of DSSC Expired - Fee Related CN102751098B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103606461A (en) * 2013-10-25 2014-02-26 殷逢宝 Preparation method for photo-anode of graphene composite solar cell
CN103606459A (en) * 2013-10-25 2014-02-26 殷逢宝 Photo-anode of graphene composite solar cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1790752A (en) * 2004-12-15 2006-06-21 中国科学院化学研究所 Preparing dye sensitized nanocrystalline semiconductor solar cell optical anode using electrical spinning method
CN101777429A (en) * 2010-02-10 2010-07-14 中国科学院上海硅酸盐研究所 Graphene-based dye-sensitized solar cell complex light anode and preparation method
CN102347143A (en) * 2011-07-11 2012-02-08 中国科学院上海硅酸盐研究所 Graphene composite porous counter electrode, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1790752A (en) * 2004-12-15 2006-06-21 中国科学院化学研究所 Preparing dye sensitized nanocrystalline semiconductor solar cell optical anode using electrical spinning method
CN101777429A (en) * 2010-02-10 2010-07-14 中国科学院上海硅酸盐研究所 Graphene-based dye-sensitized solar cell complex light anode and preparation method
CN102347143A (en) * 2011-07-11 2012-02-08 中国科学院上海硅酸盐研究所 Graphene composite porous counter electrode, preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103606461A (en) * 2013-10-25 2014-02-26 殷逢宝 Preparation method for photo-anode of graphene composite solar cell
CN103606459A (en) * 2013-10-25 2014-02-26 殷逢宝 Photo-anode of graphene composite solar cell
CN103606461B (en) * 2013-10-25 2016-07-06 殷逢宝 A kind of preparation method of the light anode of Graphene composite solar battery
CN103606459B (en) * 2013-10-25 2016-08-17 殷逢宝 A kind of light anode of Graphene composite solar battery

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