CN102610392A - Metal selenide counter-electrode for dye-sensitized solar cell and preparation method of metal selenide counter-electrode - Google Patents

Metal selenide counter-electrode for dye-sensitized solar cell and preparation method of metal selenide counter-electrode Download PDF

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CN102610392A
CN102610392A CN2012100759569A CN201210075956A CN102610392A CN 102610392 A CN102610392 A CN 102610392A CN 2012100759569 A CN2012100759569 A CN 2012100759569A CN 201210075956 A CN201210075956 A CN 201210075956A CN 102610392 A CN102610392 A CN 102610392A
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electrode
counter
metal selenide
water heating
preparation
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王忠胜
宫峰
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Fudan 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

Abstract

The invention belongs to the technical field of solar cells, and particularly discloses a metal selenide counter-electrode for a dye-sensitized solar cell and a preparation method of the metal selenide counter-electrode. The preparation method includes preparing metal selenide by the aid of a one-step hydrothermal synthesis method; realizing in-situ growth of the metal selenide on a conducting substrate without any other aftertreatment; and directly applying the metal selenide to the dye-sensitized solar cell so that better energy conversion efficiency can be obtained as compared with a pyrolysis platinum counter-electrode. A process is simple, the prepared non-platinum counter-electrode not only is high in catalytic activity, but also is cheap in price, the cost of the counter-electrode is greatly reduced, furthermore, the comprehensive cost of the dye-sensitized solar cell is reduced, and the metal selenide counter-electrode and the preparation method can be applied to large-scale industrial production of dye-sensitized solar cells.

Description

The used by dye sensitization solar battery metal selenide is to electrode and preparation method thereof
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of metal selenide that is applied to DSSC electrode and preparation method thereof.
Background technology
Since M. Gr professor tzel in 1991 introduces dye sensitization broad stopband TiO with the notion of nanoporous 2In the semiconducter research; Obtain energy conversion efficiency 7.1 % dye-sensitized solar cells (dye-sensitized solar cells, DSSCs) since (Nature, 1991; 353; 737), DSSCs obtains international academia and industrial quarters extensive concern rapidly with its low cost, simple relatively manufacture craft, higher characteristics such as electricity conversion.
DSSCs mainly forms by the porous semi-conductor nano-crystal film of dye sensitization, electrolyte with to electrode.Dye molecule excites after receiving illumination, and electronics injects the conduction band of semiconductive thin film, and electronics is got back to electrode through external circuit, I 3 -Ion obtains electronics generation I on to electrode -Ion, I -Ions diffusion restores the oxidation state dyestuff to semiconductive thin film, make dyestuff regeneration, I -Regeneration I after the ionic reaction 3 -Ion, so circulation, thus realize opto-electronic conversion.In this process, reduce because above-mentioned reduction reaction is being very necessary to the energy consumption on the electrode.Therefore, as one of them important component part, to the catalytic performance of electrode electricity conversion important influence to DSSCs.Platinum adopts magnetron sputtering (Electrochimi. Acta., 2001,46 usually to electrode; 3457) and chloroplatinic acid thermal decomposition (J. Electrochem. Soc., 1997,144; 876) method makes, though catalysis performance preferably and combination property are arranged, because platinum is noble metal; And preparation method's height that consumes energy, these methods have tangible limitation if be used for large-scale production.Therefore the non-platinum of development of new, cheapness and have higher catalytic activity to electrode, be the focus of the research in DSSCs field in recent years.
Many inorganic compounds have characteristics such as corrosion-resistant, that conductivity is good, have electrochemical catalysis activity preferably.Many relevant reports were also arranged in recent years, like CoS (J. Am. Chem. Soc., 2009,131; 15976), TiN (Chem. Comm., 2009,47; 6720), MoC (Angew. Chem. Int. Ed., 2011,50; 3582) etc., all obtained higher photoelectric conversion efficiency, but these methods need loaded down with trivial details experimental facilities or high temperature sintering mostly; Preparation condition is comparatively harsh, needs higher production cost equally, therefore efficiently electrode material is had important application value through simple method preparation.
Summary of the invention
Drawback such as high to the electrode cost to traditional platinum, that power consumption is big the objective of the invention is to propose a kind of cost is low, power consumption is little used by dye sensitization solar battery to electrode and preparation method thereof.
Used by dye sensitization solar battery provided by the invention is to electrode, and its material is a metal selenide.The preparation process of this metal selenide is:
(1) slaine and selenium powder are added in the water heating kettle, add hydrazine hydrate solution again, add suitable quantity of water at last, mixeding liquid volume is reached about about 3/4 capacity of water heating kettle;
(2) stir, in water heating kettle, put into a conductive substrates then, carry out hydro-thermal reaction after the water heating kettle envelope is tight through cleaning;
(3) after reaction finished, water heating kettle naturally cooled to room temperature, took out conductive substrates, and drip washing is clean, dries up.The gained material can be directly as electrode is applied to DSSC.
Among the above-mentioned preparation method; Described slaine is hydrochloride, acetate or the nitrate etc. of cobalt (Co), nickel (Ni) or copper metals such as (Cu); The mol ratio of metal ion and selenium powder is 1:0.01 ~ 1:100, and the mol ratio of metal ion and hydrazine hydrate is 1:0.01 ~ 1:100; Said conductive substrates is materials such as electro-conductive glass or conductive polymer membrane; Said hydrothermal temperature is 100 ℃ ~ 240 ℃, and the reaction time is 2h ~ 120h.
According to the present invention preparation to electrode, energy conversion efficiency surpasses pyrolysis platinum to electrode, and technology of the present invention is simple, Co, Ni etc. is cheap metal, can reduce the manufacturing cost to electrode and even DSSCs greatly, is suitable for the large-scale production of DSSCs.
Description of drawings
Fig. 1 is the Co of preparation in the embodiment of the invention 1 and 2 0.85Se and Ni 0.85Se is to the stereoscan photograph of electrode.
Fig. 2 is the Co of preparation in the embodiment of the invention 1 and 2 0.85Se and Ni 0.85(effective area is 0.2304 cm to Se to the current-voltage curve figure of the DSSCs compare test of electrode assembling to electrode and pyrolysis platinum 2).
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1, with 0.1 mmol cobalt chloride hexahydrate (CoCl 26H 2O) and 0.15 mmol selenium powder (purity 99.999%) add in the 50 mL water heating kettles, add 7.5 mL hydrazine hydrate solutions (content 85wt%) again, add 30 mL deionized waters at last, make mixeding liquid volume reach about 3/4 capacity of water heating kettle.After stirring, in water heating kettle, put into a FTO electro-conductive glass that thoroughly cleans, after the water heating kettle envelope is tight, 120 ℃ of hydro-thermal reaction 12 h.Reaction finishes the back water heating kettle and naturally cools to room temperature, takes out electro-conductive glass, dries up after drip washing is clean.
According to standard method this is assembled into DSSCs to electrode, cell area is 0.2304 cm 2Under the AM1.5 simulated solar irradiation, record current-voltage (I-V) curve (shown in Fig. 2 curve 1) of DSSC, the photovoltage that obtains opening a way ( V Oc ) be 739 mV, short-circuit photocurrent ( J Sc ) be 16.98 mA/cm 2, fill factor, curve factor ( FF) be 0.75, energy conversion efficiency ( η) be 9.40%.
Embodiment 2, with 0.2 mmol Nickel dichloride hexahydrate (NiCl 26H 2O) and 0.24 mmol selenium powder (purity 99.999%) add in the 50 mL water heating kettles, add 15 mL hydrazine hydrate solutions (content 85wt%) again, add 22.5 mL deionized waters at last, make mixeding liquid volume reach about 3/4 capacity of water heating kettle.After stirring, in water heating kettle, put into a FTO electro-conductive glass that thoroughly cleans, after the water heating kettle envelope is tight, 140 ℃ of hydro-thermal reaction 10 h.Reaction finishes the back water heating kettle and naturally cools to room temperature, takes out electro-conductive glass, dries up after drip washing is clean.
According to standard method this is assembled into DSSCs to electrode, cell area is 0.2304 cm 2Under the AM1.5 simulated solar irradiation, record the I-V curve (shown in Fig. 2 curve 2) of DSSC, obtain V Oc Be 738 mV, J Sc Be 15.63 mA/cm 2, FFBe 0.72, ηBe 8.32%.
Embodiment 3, with 0.2 mmol CoCl 26H 2O and 0.4 mmol selenium powder (purity 99.999%) add in the 50 mL water heating kettles, add 20 mL hydrazine hydrate solutions (content 85wt%) again, add 17.5 mL deionized waters at last, make mixeding liquid volume reach about 3/4 capacity of water heating kettle.After stirring, in water heating kettle, put into a FTO electro-conductive glass that thoroughly cleans, after the water heating kettle envelope is tight, 100 ℃ of hydro-thermal reaction 24 h.Reaction finishes the back water heating kettle and naturally cools to room temperature, takes out electro-conductive glass, dries up after drip washing is clean.
According to standard method this is assembled into DSSCs to electrode, cell area is 0.2304 cm 2Under the AM1.5 simulated solar irradiation, record the I-V curve of DSSC, obtain V Oc Be 722 mV, J Sc Be 14.74 mA/cm 2, FFBe 0.74, ηBe 7.88 %.
Embodiment 4, with 0.3 mmol NiCl 26H 2O and 0.4 mmol selenium powder (purity 99.999%) add in the 50 mL water heating kettles, add 30 mL hydrazine hydrate solutions (content 85wt%) again, add 7.5 mL deionized waters at last, make mixeding liquid volume reach about 3/4 capacity of water heating kettle.After stirring, in water heating kettle, put into a FTO electro-conductive glass that thoroughly cleans, after the water heating kettle envelope is tight, 150 ℃ of hydro-thermal reaction 6 h.Reaction finishes the back water heating kettle and naturally cools to room temperature, takes out electro-conductive glass, dries up after drip washing is clean.
According to standard method this is assembled into DSSCs to electrode, cell area is 0.2304 cm 2Under the AM1.5 simulated solar irradiation, record the I-V curve of DSSC, obtain V Oc Be 706 mV, J Sc Be 14.77 mA/cm 2, FFBe 0.68, ηBe 7.09 %.
Embodiment 5, with 0.1 mmol anhydrous cupric chloride (CuCl 2) and 0.15 mmol selenium powder (purity 99.999%) add in the 50 mL water heating kettles, add 10 mL hydrazine hydrate solutions (content 85wt%) again, add 27.5 mL deionized waters at last, make mixeding liquid volume reach about 3/4 capacity of water heating kettle.After stirring, in water heating kettle, put into a FTO electro-conductive glass that thoroughly cleans, after the water heating kettle envelope is tight, 180 ℃ of hydro-thermal reaction 12 h.Reaction finishes the back water heating kettle and naturally cools to room temperature, takes out electro-conductive glass, dries up after drip washing is clean.
According to standard method this is assembled into DSSCs to electrode, cell area is 0.2304 cm 2Under the AM1.5 simulated solar irradiation, record the I-V curve of DSSC, obtain V Oc Be 660 mV, J Sc Be 10.81 mA/cm 2, FFBe 0.41, ηBe 2.93 %.
Comparative example, as comparing, we also under the identical situation of every other condition, adopt pyrolysis platinum that electrode has been assembled DSSC, under AM 1.5 simulated solar irradiations, record the I-V curve (shown in Fig. 2 curve 3) of DSSC, obtain V Oc Be 738 mV, J Sc Be 16.03 mA/cm 2, FFBe 0.74, ηBe 8.64 %.
Co according to the embodiment of the invention 1 preparation 0.85Se is to electrode, and energy conversion efficiency has surpassed pyrolysis platinum to electrode, the Ni of embodiment 2 preparations 0.85Se can obtain the photovoltaic performance suitable with pyrolysis platinum to electrode.Technology of the present invention is simple, and Co, Ni are cheap metal, thereby greatly reduces the manufacturing cost to electrode and even DSSCs, can be applicable to the production of extensive DSSCs.

Claims (2)

1. the genus selenides of a used by dye sensitization solar battery is characterized in that to the preparation method of electrode concrete steps are:
(1) slaine and selenium powder are added in the water heating kettle, add hydrazine hydrate solution again, add suitable quantity of water at last;
(2) stir, in water heating kettle, put into conductive substrates then, carry out hydro-thermal reaction after the water heating kettle envelope is tight through cleaning;
(3) after reaction finished, water heating kettle naturally cooled to room temperature, took out conductive substrates, and drip washing is clean, dries up;
Wherein, described slaine is hydrochloride, acetate or the nitrate of cobalt, nickel or copper metal, and the mol ratio of metal ion and selenium powder is 1:0.01 ~ 1:100, and the mol ratio of metal ion and hydrazine hydrate is 1:0.01 ~ 1:100; Said conductive substrates is materials such as electro-conductive glass or conductive polymer membrane; Said hydrothermal temperature is 100 ℃ ~ 240 ℃, and the reaction time is 2h ~ 120h.
According to claim 1 the metal selenide that is applied to DSSC of method preparation to electrode material.
CN2012100759569A 2012-03-21 2012-03-21 Metal selenide counter-electrode for dye-sensitized solar cell and preparation method of metal selenide counter-electrode Pending CN102610392A (en)

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CN102915851A (en) * 2012-11-14 2013-02-06 中国科学院青岛生物能源与过程研究所 Dye-sensitized solar cell counter electrode based on selenide
CN104269565A (en) * 2014-08-18 2015-01-07 广州大学 Preparation method and use of multiwalled carbon nanotube (MWCNT)-loaded Ni0.85Se composite material
CN105957723A (en) * 2016-05-31 2016-09-21 浙江大学 Method for preparing cobaltous selenide super-capacitor material through chemical vapor deposition method
CN106057480A (en) * 2016-08-11 2016-10-26 浙江大学 Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof
CN106206042A (en) * 2016-08-10 2016-12-07 三峡大学 A kind of DSSC NiSe preparation method to electrode
CN106971849A (en) * 2017-05-22 2017-07-21 阜阳师范学院 NiSe electrocatalysis materials and its production and use
CN107680814A (en) * 2017-09-01 2018-02-09 淮阴工学院 The Ni-based selenides photonic crystal of cobalt/nickel cobalt for DSSC is to electrode
CN108364792A (en) * 2018-01-24 2018-08-03 复旦大学 A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material
CN108376612A (en) * 2018-01-24 2018-08-07 复旦大学 Preparation method of the used by dye sensitization solar battery graphene/nickelous selenide to electrode
CN108630438A (en) * 2017-03-24 2018-10-09 丰田自动车株式会社 Cobaltous selenide/titanium net decomposes water oxygen electrode and preparation method thereof
CN108878153A (en) * 2018-06-28 2018-11-23 福州大学 A kind of ferrous selenide nickel dye-sensitized solar cells is to electrode
CN108987117A (en) * 2018-07-04 2018-12-11 阜阳师范学院 CoSe2The preparation method of electrocatalysis material and its application in two-sided quasi-solid-state dye sensitized solar battery
CN110548525A (en) * 2019-09-21 2019-12-10 台州学院 Preparation method of carbon nanotube composite nickel-selenium nanosheet electrocatalyst
CN112735835A (en) * 2021-01-21 2021-04-30 福州大学 Vanadium diselenide-doped nickel-cobalt selenide yolk shell structure micro cuboid counter electrode catalyst and preparation method and application thereof

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Cited By (22)

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CN102915851B (en) * 2012-11-14 2016-01-20 中国科学院青岛生物能源与过程研究所 A kind of DSSC based on selenides is to electrode
CN102915851A (en) * 2012-11-14 2013-02-06 中国科学院青岛生物能源与过程研究所 Dye-sensitized solar cell counter electrode based on selenide
CN104269565A (en) * 2014-08-18 2015-01-07 广州大学 Preparation method and use of multiwalled carbon nanotube (MWCNT)-loaded Ni0.85Se composite material
CN104269565B (en) * 2014-08-18 2017-02-22 广州大学 Preparation method and use of multiwalled carbon nanotube (MWCNT)-loaded Ni0.85Se composite material
CN105957723A (en) * 2016-05-31 2016-09-21 浙江大学 Method for preparing cobaltous selenide super-capacitor material through chemical vapor deposition method
CN106206042A (en) * 2016-08-10 2016-12-07 三峡大学 A kind of DSSC NiSe preparation method to electrode
CN106057480A (en) * 2016-08-11 2016-10-26 浙江大学 Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof
CN106057480B (en) * 2016-08-11 2018-06-01 浙江大学 Three-dimensional porous selenides nanocomposite for ultracapacitor and preparation method thereof
CN108630438A (en) * 2017-03-24 2018-10-09 丰田自动车株式会社 Cobaltous selenide/titanium net decomposes water oxygen electrode and preparation method thereof
CN106971849A (en) * 2017-05-22 2017-07-21 阜阳师范学院 NiSe electrocatalysis materials and its production and use
CN107680814A (en) * 2017-09-01 2018-02-09 淮阴工学院 The Ni-based selenides photonic crystal of cobalt/nickel cobalt for DSSC is to electrode
CN107680814B (en) * 2017-09-01 2018-11-13 淮阴工学院 For the cobalt-based of dye-sensitized solar cells or the Ni-based selenides photonic crystal of Ni-based or cobalt to electrode
CN108364792A (en) * 2018-01-24 2018-08-03 复旦大学 A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material
CN108376612A (en) * 2018-01-24 2018-08-07 复旦大学 Preparation method of the used by dye sensitization solar battery graphene/nickelous selenide to electrode
CN108364792B (en) * 2018-01-24 2020-04-24 复旦大学 Preparation method and application of nickel-cobalt-selenium hollow spherical multilevel structure material
CN108878153A (en) * 2018-06-28 2018-11-23 福州大学 A kind of ferrous selenide nickel dye-sensitized solar cells is to electrode
CN108878153B (en) * 2018-06-28 2019-09-13 福州大学 A kind of ferrous selenide nickel dye-sensitized solar cells is to electrode
CN108987117A (en) * 2018-07-04 2018-12-11 阜阳师范学院 CoSe2The preparation method of electrocatalysis material and its application in two-sided quasi-solid-state dye sensitized solar battery
CN110548525A (en) * 2019-09-21 2019-12-10 台州学院 Preparation method of carbon nanotube composite nickel-selenium nanosheet electrocatalyst
CN110548525B (en) * 2019-09-21 2022-02-25 台州学院 Preparation method of carbon nanotube composite nickel-selenium nanosheet electrocatalyst
CN112735835A (en) * 2021-01-21 2021-04-30 福州大学 Vanadium diselenide-doped nickel-cobalt selenide yolk shell structure micro cuboid counter electrode catalyst and preparation method and application thereof
CN112735835B (en) * 2021-01-21 2021-09-28 福州大学 Vanadium diselenide-doped nickel-cobalt selenide yolk shell structure micro cuboid counter electrode catalyst and preparation method and application thereof

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