CN102768908A - Energy storage dye sensitization solar battery and preparation method thereof - Google Patents

Energy storage dye sensitization solar battery and preparation method thereof Download PDF

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Publication number
CN102768908A
CN102768908A CN2012102537642A CN201210253764A CN102768908A CN 102768908 A CN102768908 A CN 102768908A CN 2012102537642 A CN2012102537642 A CN 2012102537642A CN 201210253764 A CN201210253764 A CN 201210253764A CN 102768908 A CN102768908 A CN 102768908A
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layer
energy storage
tio
accumulate
dssc
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李学良
张波
肖正辉
陈洁洁
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Hefei University of Technology
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Hefei University of 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
    • 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 an energy storage dye sensitization solar battery and a preparation method thereof. A top conductive glass substrate (1), a TiO2 electricity storage layer (2), a first electrolyte layer (3), a diaphragm (4), a second electrolyte layer (5), an electricity storage layer (6) and a bottom conductive glass substrate (7) are sequentially arranged on the solar battery from top to bottom. Compared with the conventional solar battery which only serves as a solar photoelectric converter, the energy storage dye sensitization solar battery does not need an external electricity storage device, integrates functions of converting light energy into electric energy and storing the electric energy on the same structure and has a non-light-energy charging function.

Description

A kind of energy storage DSSC and preparation method thereof
One, technical field
The present invention relates to a kind of solar cell and preparation method thereof, specifically a kind of energy storage DSSC and preparation method thereof belongs to energy technology field.
Two, background technology
Along with the energy and environmental crisis are serious day by day, seeking the new reproducible energy is becoming a problem demanding prompt solution.People have carried out multinomial research, are intended to develop the alternative energy, thereby can substitute traditional fossil fuel, and the energy crisis that benefit is closed on is said in solution.Solar energy is inexhaustible, and green renewable.
DSSC is an electrochemistry solar energy battery, its main composition by: absorb visible light and produce the right light-sensitive coloring agent molecule in electronics one hole and transmit the transition metal oxide of generation electronics.
But; Existing solar cell is a light energy converter, is conversion of solar energy electric energy output only, when having sunlight, can't not export energy; How research to solar energy at present also only just improves conversion ratio; Storage for electric energy only is the energy storage device that externally adds a simple function, and device is not portable owing to adding, and has directly limited the development of solar cell miniaturization.
Three, summary of the invention
The present invention aims to provide a kind ofly has opto-electronic conversion and two kinds of functions of energy storage in energy storage DSSC of one and preparation method thereof simultaneously; When making solar cell that luminous energy is converted into electric energy; Can a part of electrical power storage be got up, a part of in addition electric energy is used for output.
Technical solution problem of the present invention adopts following technical scheme:
Energy storage DSSC of the present invention is characterized in that this solar cell is disposed with from top to bottom: end face Conducting Glass 1, TiO 2Accumulate layer 2, first electrolyte layer 3, barrier film 4, second electrolyte layer 5, accumulate layer 6 and bottom surface Conducting Glass 7; To contain TiO 2The end face Conducting Glass 1 of accumulate layer 2 with contain accumulate layer 6 bottom surface Conducting Glass 7 as to electrode;
Said TiO 2Accumulate layer 2 is with TiO 2With energy storage material sputter at after by mass ratio 5:10-24 mixing and ball milling be immersed in subsequently on the conducting surface of end face Conducting Glass 1 in the dye solution 24 hours and vacuumize after the TiO that forms 2Accumulate layer 2;
Said accumulate layer 6 is with the energy storage material spraying or is deposited on the accumulate layer 6 that forms on the conducting surface of bottom surface Conducting Glass 7);
Said TiO 2Be nanometer porous TiO 2, said energy storage material is selected from material with carbon element, polyaniline compound material or metal oxide.
Said material with carbon element is the nanometer spherical material with carbon element through the charcoal-aero gel preparation;
Said metal oxide is selected from MnO 2, NiO or Ni 2O 3
Said polyaniline compound material is a polyaniline;
Said dyestuff is selected from N3, N719 or C106.
Said TiO 2The thickness of accumulate layer 2 is 500-2000 μ m.
Said first electrolyte layer 3 and second electrolyte layer 5 are made up of liquid electrolyte, and said liquid electrolyte is the mixture that the ratio of a kind of and monomethyl triethyl group ammonium tetrafluoroborate, a kind of 1:1 by volume in the tetraethyl ammonium tetrafluoroborate in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, the methyl ethyl carbonate forms.
Said barrier film 4 is selected from polypropylene screen, diaphragm paper or macromolecule pellicle.
The preparation method of energy storage DSSC of the present invention, operation as follows:
A, with TiO 2With energy storage material mix be incorporated in 400-800 ℃ of ball milling 1-3 hour compound, said compound is sputtered on the conducting surface of end face Conducting Glass 1 through mixing sputtering method then, be immersed in the dyestuff 24 hours subsequently and vacuumize forms TiO 2Accumulate layer 2;
B, be not higher than under 300 ℃ the condition the energy storage material spraying in temperature or be deposited on bottom surface Conducting Glass 7) conducting surface on form accumulate layer 6;
C, at TiO 2Insert barrier film 4 between accumulate layer 2 and the accumulate layer 6, inject liquid electrolyte after the pressing, respectively at TiO 2Form first electrolyte layer 3 between accumulate layer 2 and the barrier film 4, formation second electrolyte layer 5 between accumulate layer 6 and barrier film 4; Will be by end face Conducting Glass 1, TiO 2The layer structure that accumulate layer 2, first electrolyte layer 3, barrier film 4, second electrolyte layer 5, accumulate layer 6 and bottom surface Conducting Glass 7 constitute seals formation energy storage DSSC in periphery.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the present invention is through adding energy storage material; Change the structure of solar cell, in solar cell, added electrolyte and barrier film simultaneously, solved the problem of electrical conductivity in the thermal energy storage process; Based on above structure; Energy storage DSSC of the present invention can get up a part of electrical power storage when luminous energy is converted into electric energy, and a part of in addition electric energy is used for output.
2, with the prepared complete energy storage DSSC of the inventive method at solar simulator irradiation individual hour of 1-4 down; Its open circuit voltage is 0.5-0.7V; The DSSC that only has opto-electronic conversion is compared; The open circuit voltage of energy storage DSSC does not reduce, and the postradiation energy storage DSSC of solar simulator dark place was placed 200-400 hour, and its open circuit voltage is 0.2-0.3V.
Four, description of drawings
Fig. 1 is the structural representation of energy storage DSSC of the present invention;
Label among the figure: 1 end face Conducting Glass; 2TiO 2The accumulate layer; 3 first electrolyte layers; 4 barrier films; 5 second electrolyte layers; 6 accumulate layers; 7 bottom surface Conducting Glass.
Five, embodiment
Embodiment 1:
With the 0.5g nano-TiO 2And the 1g carbosphere got compound in 3 hours at 400 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent C106 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 500 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide NiO on bottom surface Conducting Glass 7 forms accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting polypropylene diaphragm 4 between accumulate layer 2 and the accumulate layer 6; Be to inject tetraethyl ammonium tetrafluoroborate and dimethyl carbonate mixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 2 hours, its open circuit voltage is 0.67V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 400 hours, and its open circuit voltage is 0.23V.The solar simulator irradiation has decayed 9.2% after simulation discharges and recharges 5000 times fast down, and measuring its open circuit voltage is 0.60V.
Embodiment 2:
With the 0.5g nano-TiO 2And the 1.2g carbosphere got compound in 2 hours at 600 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent C106 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 700 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
On bottom surface Conducting Glass 7, spray polyaniline, form accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting polypropylene diaphragm 4 between accumulate layer 2 and the accumulate layer 6; Be to inject monomethyl triethyl group ammonium tetrafluoroborate and dimethyl carbonate mixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy-storage solar battery.
After 2 hours, its open circuit voltage is 0.70V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 380 hours, and its open circuit voltage is 0.26V.
Embodiment 3:
With the 0.5g nano-TiO 2And the 1.4g carbosphere got compound in 1 hour at 800 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent C106 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 900 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide M nO on bottom surface Conducting Glass 7 2, form accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting polypropylene diaphragm 4 between accumulate layer 2 and the accumulate layer 6; Be to inject tetraethyl ammonium tetrafluoroborate and diethyl carbonate mixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 2.5 hours, its open circuit voltage is 0.69V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 350 hours, and its open circuit voltage is 0.22V.
Embodiment 4:
With the 0.5g nano-TiO 2And the 1.6g carbosphere got compound in 2 hours at 700 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent N719 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 1100 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide Ni on bottom surface Conducting Glass 7 2O 3, form accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting macromolecule pellicle 4 between accumulate layer 2 and the accumulate layer 6; Be to inject monomethyl triethyl group ammonium tetrafluoroborate and diethyl carbonate mixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 2.5 hours, its open circuit voltage is 0.67V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 400 hours, and its open circuit voltage is 0.23V.
Embodiment 5:
With the 0.5g nano-TiO 2And the 1.8g carbosphere got compound in 2 hours at 600 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent N719 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 1300 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide NiO on bottom surface Conducting Glass 7 forms accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting macromolecule pellicle 4 between accumulate layer 2 and the accumulate layer 6; Be to inject tetraethyl ammonium tetrafluoroborate and propylene carbonate ester admixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 3 hours, its open circuit voltage is 0.70V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 370 hours, and its open circuit voltage is 0.21V.
Embodiment 6:
With the 0.5g nano-TiO 2And the 2g carbosphere got compound in 3 hours at 600 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent N719 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 1500 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide Ni on bottom surface Conducting Glass 7 2O 3, form accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting macromolecule pellicle 4 between accumulate layer 2 and the accumulate layer 6; Be to inject monomethyl triethyl group ammonium tetrafluoroborate and propylene carbonate ester admixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 3 hours, its open circuit voltage is 0.67V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 360 hours, and its open circuit voltage is 0.25V.
Embodiment 7:
With the 0.5g nano-TiO 2And the 2.2g carbosphere got compound in 3 hours at 400 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent N3 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 1700 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
Spray metal oxide NiO on bottom surface Conducting Glass 7 forms accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting diaphragm paper 4 between accumulate layer 2 and the accumulate layer 6; Be to inject tetraethyl ammonium tetrafluoroborate and ethylene carbonate ester admixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 3.5 hours, its open circuit voltage is 0.68V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 370 hours, and its open circuit voltage is 0.23V.
Embodiment 8:
With the 0.5g nano-TiO 2And the 2.4g carbosphere got compound in 3 hours at 400 ℃ of following ball millings; Compound is splashed on the conducting surface of end face Conducting Glass 1 through mixing sputtering method; In the light-sensitive coloring agent N3 of 0.3mmol/L solution, soaked 24 hours subsequently, it is the TiO of 2000 μ m that the taking-up final vacuum dries formation thickness 2Accumulate layer 2;
On bottom surface Conducting Glass 7, spray polyaniline, form accumulate layer 6 with 300 ℃ of sintering, at TiO 2Carry out pressing after inserting diaphragm paper 4 between accumulate layer 2 and the accumulate layer 6; Be to inject monomethyl triethyl group ammonium tetrafluoroborate and ethylene carbonate ester admixture at 1: 1 more by volume in the device of pressing; Form first electrolyte layer 3 and second electrolyte layer 5 respectively; Seal in the periphery of device then, form the energy storage DSSC.
After 4 hours, its open circuit voltage is 0.70V to the prepared energy storage DSSC of present embodiment in the solar simulator irradiation; Postradiation energy storage DSSC dark place was placed 350 hours, and its open circuit voltage is 0.25V.

Claims (6)

1. an energy storage DSSC is characterized in that this solar cell is disposed with from top to bottom: end face Conducting Glass (1), TiO 2Accumulate layer (2), first electrolyte layer (3), barrier film (4), second electrolyte layer (5), accumulate layer (6) and bottom surface Conducting Glass (7);
Said TiO 2Accumulate layer (2) is with TiO 2With energy storage material sputter at after by mass ratio 5:10-24 mixing and ball milling be immersed in subsequently on the conducting surface of end face Conducting Glass (1) in the dye solution 24 hours and vacuumize after the TiO that forms 2Accumulate layer (2);
Said accumulate layer (6) is with the energy storage material spraying or is deposited on the accumulate layer (6) that forms on the conducting surface of bottom surface Conducting Glass (7);
Said TiO 2Be nanometer porous TiO 2, said energy storage material is selected from material with carbon element, polyaniline compound material or metal oxide.
2. energy storage DSSC according to claim 1 is characterized in that:
Said material with carbon element is the nanometer spherical material with carbon element;
Said metal oxide is selected from MnO 2, NiO or Ni 2O 3
Said polyaniline compound material is a polyaniline;
Said dyestuff is selected from N3, N719 or C106.
3. energy storage DSSC according to claim 1 is characterized in that:
Said TiO 2The thickness of accumulate layer (2) is 500-2000 μ m.
4. energy storage DSSC according to claim 1 is characterized in that:
Said first electrolyte layer (3) and second electrolyte layer (5) are made up of liquid electrolyte, and said liquid electrolyte is the mixture that the ratio of a kind of and monomethyl triethyl group ammonium tetrafluoroborate, a kind of 1:1 by volume in the tetraethyl ammonium tetrafluoroborate in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, the methyl ethyl carbonate forms.
5. energy storage DSSC according to claim 1 is characterized in that:
Said barrier film (4) is selected from polypropylene screen, diaphragm paper or macromolecule pellicle.
6. the preparation method of the described energy storage DSSC of claim 1 is characterized in that operating as follows:
A, with TiO 2With energy storage material mix be incorporated in 400-800 ℃ of ball milling 1-3 hour compound, said compound is sputtered on the conducting surface of end face Conducting Glass (1) through mixing sputtering method then, be immersed in the dyestuff 24 hours subsequently and vacuumize forms TiO 2Accumulate layer (2);
B, be not higher than under 300 ℃ the condition the energy storage material spraying in temperature or be deposited on the conducting surface of bottom surface Conducting Glass (7) and form accumulate layer (6);
C, at TiO 2Insert barrier film (4) between accumulate layer (2) and the accumulate layer (6), inject liquid electrolyte after the pressing, respectively at TiO 2Form first electrolyte layer (3) between accumulate layer (2) and the barrier film (4), between accumulate layer (6) and barrier film (4), form second electrolyte layer (5); Will be by end face Conducting Glass (1), TiO 2The layer structure that accumulate layer (2), first electrolyte layer (3), barrier film (4), second electrolyte layer (5), accumulate layer (6) and bottom surface Conducting Glass (7) constitute seals in periphery and forms the energy storage DSSC.
CN2012102537642A 2012-07-20 2012-07-20 Energy storage dye sensitization solar battery and preparation method thereof Pending CN102768908A (en)

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CN103295796A (en) * 2013-05-31 2013-09-11 合肥工业大学 Energy-stored photovoltaic battery and manufacturing method thereof
CN103337370A (en) * 2013-05-31 2013-10-02 合肥工业大学 Energy storage photosensitive solar energy cell anode and preparation method thereof
CN104409217A (en) * 2014-11-24 2015-03-11 常州大学 Photocathode and solar cell with same
CN105551804A (en) * 2016-01-28 2016-05-04 常州大学 Photocathode and quantum dot-sensitized solar cell comprising same
CN107275095A (en) * 2017-06-09 2017-10-20 中国科学院武汉物理与数学研究所 A kind of compound lithium rechargeable battery that can be charged with dye sensitization of solar
CN110323070A (en) * 2019-07-12 2019-10-11 长春工业大学 A kind of light auxiliary charging battery based on difunctional compatible electrode
CN111244584A (en) * 2020-01-10 2020-06-05 国网江西省电力有限公司电力科学研究院 Light charging polymer secondary battery and manufacturing method thereof

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CN102290257A (en) * 2011-05-19 2011-12-21 内蒙古大学 Method for preparing dye sensitized solar cell with selective light transmission
CN102468055A (en) * 2010-11-15 2012-05-23 海洋王照明科技股份有限公司 Layered adsorption dye-sensitized solar battery and preparation method thereof

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EP2230702A1 (en) * 2009-03-19 2010-09-22 Ecole Polytechnique Fédérale de Lausanne (EPFL) Modified surface
CN101857191A (en) * 2010-04-16 2010-10-13 华侨大学 Flexible transduction/energy-storage nanodevice and preparation method
CN102468055A (en) * 2010-11-15 2012-05-23 海洋王照明科技股份有限公司 Layered adsorption dye-sensitized solar battery and preparation method thereof
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103295796A (en) * 2013-05-31 2013-09-11 合肥工业大学 Energy-stored photovoltaic battery and manufacturing method thereof
CN103337370A (en) * 2013-05-31 2013-10-02 合肥工业大学 Energy storage photosensitive solar energy cell anode and preparation method thereof
CN103295796B (en) * 2013-05-31 2015-09-30 合肥工业大学 A kind of energy storage photovoltaic cell and preparation method thereof
CN103337370B (en) * 2013-05-31 2016-06-08 合肥工业大学 A kind of energy storage photosensitized solar cell positive pole and preparation method thereof
CN104409217A (en) * 2014-11-24 2015-03-11 常州大学 Photocathode and solar cell with same
CN105551804A (en) * 2016-01-28 2016-05-04 常州大学 Photocathode and quantum dot-sensitized solar cell comprising same
CN107275095A (en) * 2017-06-09 2017-10-20 中国科学院武汉物理与数学研究所 A kind of compound lithium rechargeable battery that can be charged with dye sensitization of solar
CN107275095B (en) * 2017-06-09 2019-02-26 中国科学院武汉物理与数学研究所 A kind of compound lithium ion secondary battery that can be charged with dye sensitization of solar
CN110323070A (en) * 2019-07-12 2019-10-11 长春工业大学 A kind of light auxiliary charging battery based on difunctional compatible electrode
CN111244584A (en) * 2020-01-10 2020-06-05 国网江西省电力有限公司电力科学研究院 Light charging polymer secondary battery and manufacturing method thereof

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Application publication date: 20121107