CN103172062B - Preparation method of graphene film for dye-sensitized solar cell counter electrodes - Google Patents
Preparation method of graphene film for dye-sensitized solar cell counter electrodes Download PDFInfo
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- CN103172062B CN103172062B CN201310132358.5A CN201310132358A CN103172062B CN 103172062 B CN103172062 B CN 103172062B CN 201310132358 A CN201310132358 A CN 201310132358A CN 103172062 B CN103172062 B CN 103172062B
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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 invention discloses a preparation method of a graphene film for dye-sensitized solar cell counter electrodes. The method comprises the following concrete steps: firstly preparing graphite oxide aqueous solution through a Hummers method, then adding N, N-dimethyl formamide (DMF) serving as dispersing agent into the graphite oxide aqueous solution to obtain stable grapheme oxide dispersion liquid through an ultrasonic stripping method, directly depositing the graphene film on a preheated conducting substrate through a spraying method, and finally reducing the graphene film through a hydrazine steam chemical reduction method and high-temperature calcination technology, so as to obtain the graphene film for counter electrodes. The graphene film prepared through the method not only has higher electrical conductivity and can effectively transmit electron, but also has the characteristics of good uniformity, low cost and high production efficiency, and can preliminarily replace expensive platinum counter electrodes.
Description
Technical field
The present invention relates to the technology of preparing of new material Graphene (Graphene) film, be specifically related to the preparation method of a kind of DSSC to electrode graphene film, belong to nanometer field of energy source materials.
Background technology
Graphene (Graphene) be by carbon atom with
sp 2the two dimensional crystal material that the monoatomic layer that hydridization connects is formed, wherein carbon atom is arranged in graphene planes with hexa-atomic annular preiodic type.In Graphene, the motion of electronics is as the motion of the theory of relativity massless particle, follows the rule of linear diffusion simultaneously, therefore causes Graphene to have the electrology characteristic of many novelties.The electric property of Graphene is highly stable, does not vary with temperature, and the impact by environment is also very little, and electron mobility is up to 10
4cm
2/ Vs.All the time, DSSC is the conductive substrates of platinum plating to electrode, although platinum has good conductive capability to electrode, as everyone knows, the use cost of platinum is high.This makes in recent years, and Graphene (Graphene) material that source is extremely enriched starts to come into one's own as the research of DSSC to electrode.Such as, high congruent people [the Electrochemistry Communications of Tsing-Hua University's stone in 2008,10 (2008) 1555 – 1558] utilize spin-coating method to prepare Graphene DSSC to electrode conductive film, achieve excellent photoelectric conversion efficiency; [Solid State Sciences such as people such as Hubei University's king's generation quick grade in 2011,13 (2011) 468 – 475] utilize suction method to prepare Graphene DSSC to electrode conductive film, also achieve excellent photoelectric conversion efficiency.But spin-coating method or suction method all large area can not prepare graphene film to electrode, the pulling film forming technology occurred subsequently can realize large-area film preparation, but the graphene solution being used to pulling film forming is reunited serious, be difficult to obtain large area, uniform graphene film.
Summary of the invention
the technical problem solved:object of the present invention is exactly for the above-mentioned deficiency to electrode graphene film present Research, provides a kind of large area, uniform graphene film of realizing to the preparation method of electrode.
technical scheme:a kind of DSSC is to the preparation method of electrode graphene film, adopt N, dinethylformamide (DMF) effectively disperses graphene oxide water solution as dispersant, then spray-on process directly deposited oxide graphene film in the conductive substrates of preheating is adopted, finally by technique oxidation graphene films such as hydrazine steam chemical reduction method and high-temperature calcinations to obtain electrode graphene film.
Concrete preparation process is: (1) first adopts Hummers method to prepare graphite oxide, adopts rotating speed 10000 rpm centrifugation gained graphite oxide and uses deionized water cyclic washing, obtaining the graphite oxide aqueous solution that concentration is 1 ~ 10 mg/mL; (2) in the graphite oxide aqueous solution, N is added, dinethylformamide (DMF) solution is as dispersant, and utilizing ultrasonic stripping method to obtain the graphene oxide water solution of stably dispersing, the power of ultrasonic oscillator is 800 W, and hyperacoustic frequency is 10 kHz; (3) utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is in the conductive substrates of 150 ~ 300 DEG C, obtains graphene oxide film; (4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 6 ~ 15 h is put into; and then in the high temperature furnace that hydrogen/argon gas is mixed gas protected, 400 ~ 500 DEG C are warming up to; be down to room temperature after being incubated 1 h, obtain DSSC to electrode graphene film.
The amount of adding DMF in described step (2) accounts for 0.1 ~ 1.0% of graphene oxide water solution volume.
In described step (3), spray gun bore is 0.2 ~ 0.4 mm, and gun slot flow velocity is 2 ~ 5 mL/min, and spray time is 5 ~ 60 s.
In described step (4), the volume basis ratio of high temperature reduction protective gas argon gas and hydrogen gas mixture is 5 ~ 9; intensification and rate of temperature fall are 0.5 ~ 5 DEG C/min, and gained DSSC is advisable at 20 ~ 300 nm to the thickness of electrode graphene film.
beneficial effect:compared with existing method for preparing graphene membrane, the present invention has following characteristics: the present invention adopts graphene oxide solution instead of graphene solution as spray solution, avoids the generation of reunion; Secondly by DMF (DMF), graphene oxide is effectively disperseed, prevent the generation of reunion further, avoid and form uneven nano structure membrane to electrode in spray deposition process.
Accompanying drawing explanation
Fig. 1 is the SEM photo to electrode graphene film adopting spray deposition to obtain;
Fig. 2 display be to electrode be the DSSC that graphene film assembles Current density-voltage (
i-V) test curve.Wherein abscissa is voltage, and unit is volt (V), and ordinate is current density, and unit is mA/cm
2.
Embodiment
Below in conjunction with example, the invention will be further described, but the present invention is not limited to following examples.
embodiment 1:
(1) first adopt Hummers method to prepare graphite oxide, centrifugation gained graphite oxide also uses deionized water cyclic washing, obtains the graphite oxide aqueous solution that concentration is 1 mg/mL;
(2) in the graphite oxide aqueous solution, the N that volumn concentration is 0.1% is added, dinethylformamide (DMF) solution is as dispersant, and utilize ultrasonic stripping method to obtain the graphene oxide water solution of stably dispersing, the power of ultrasonic oscillator is 800 W, and hyperacoustic frequency is 10 kHz;
(3) regulate spray gun bore to be 0.2 mm, flow velocity is 2 mL/min, and utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is that in the ITO electro-conductive glass substrate of 150 DEG C, spray time is 5 s, obtains graphene oxide film;
(4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 6 h is put into; and then be slowly be warming up to 400 DEG C in the mixed gas protected high temperature furnace of hydrogen/argon gas of 5 in percent by volume; slowly be down to room temperature after being incubated 1 h, obtaining thickness is that the DSSC of 20 nm is to electrode graphene film.
embodiment 2:
(1) first adopt Hummers method to prepare graphite oxide, centrifugation gained graphite oxide also uses deionized water cyclic washing, obtains the graphite oxide aqueous solution that concentration is 3 mg/mL;
(2) in the graphite oxide aqueous solution, the N that volumn concentration is 0.5% is added, dinethylformamide (DMF) solution is as dispersant, and utilize ultrasonic stripping method to obtain the graphene oxide water solution of stably dispersing, the power of ultrasonic oscillator is 800 W, and hyperacoustic frequency is 10 kHz;
(3) regulate spray gun bore to be 0.3 mm, flow velocity is 3 mL/min, and utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is that in the ITO electro-conductive glass substrate of 200 DEG C, spray time is 20 s, obtains graphene oxide film;
(4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 6 h is put into; and then be slowly be warming up to 450 DEG C in the mixed gas protected high temperature furnace of hydrogen/argon gas of 6 in percent by volume; slowly be down to room temperature after being incubated 1 h, obtaining thickness is that the DSSC of 100 nm is to electrode graphene film.
embodiment 3:
(1) Hummers method is first adopted to prepare graphite oxide, centrifugation gained graphite oxide also uses deionized water cyclic washing, obtain the graphite oxide aqueous solution that concentration is 5 mg/mL, the power of ultrasonic oscillator is 800 W, and hyperacoustic frequency is 10 kHz;
(2) add in the graphite oxide aqueous solution volumn concentration be DMF (DMF) solution of 0.5% as dispersant, and utilize ultrasonic stripping method to obtain stably dispersing and the less graphene oxide water solution of the number of plies;
(3) regulate spray gun bore to be 0.4 mm, flow velocity is 3 mL/min, and utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is that in the ITO electro-conductive glass substrate of 300 DEG C, spray time is 30 s, obtains graphene oxide film;
(4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 12 h is put into; and then be slowly be warming up to 500 DEG C in the mixed gas protected high temperature furnace of hydrogen/argon gas of 9 in percent by volume; slowly be down to room temperature after being incubated 1 h, obtaining thickness is that the DSSC of 150 nm is to electrode graphene film.Fig. 1 display be that the graphene film that obtains of embodiment 3 is to scanning electron microscopy (SEM) photo of electrode.
embodiment 4:
(1) Hummers method is first adopted to prepare graphite oxide, centrifugation gained graphite oxide also uses deionized water cyclic washing, obtain the graphite oxide aqueous solution that concentration is 10 mg/mL, the power of ultrasonic oscillator is 800 W, and hyperacoustic frequency is 10 kHz;
(2) add in the graphite oxide aqueous solution volumn concentration be DMF (DMF) solution of 1.0% as dispersant, and utilize ultrasonic stripping method to obtain stably dispersing and the less graphene oxide water solution of the number of plies;
(3) regulate spray gun bore to be 0.4 mm, flow velocity is 5 mL/min, and utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is that in the ITO electro-conductive glass substrate of 300 DEG C, spray time is 60 s, obtains graphene oxide film;
(4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 15 h is put into; and then be slowly be warming up to 500 DEG C in the mixed gas protected high temperature furnace of hydrogen/argon gas of 9 in percent by volume; slowly be down to room temperature after being incubated 1 h, obtaining thickness is that the DSSC of 300 nm is to electrode graphene film.
embodiment 5:
Sprayed deposit Graphene of the present invention becomes DSSC to electrode assembling and carries out the experiment of photoelectric conversion efficiency test: by TiO
2film light anode is immersed in sensitization in the N719 dyestuff of 0.3 mmol/L, is incubated 1 h at 60 DEG C; Be that the Surlyn heat-sealing film of 60 μm is by TiO with thickness after sensitization
2the graphene film that film light anode and embodiment 3 prepare/ITO electro-conductive glass is packaged into sandwich structure, and sandwich of layers perfusion is containing the DHS-E23 type electrolyte of iodide ion; Adopt U.S. Oriel 94022A solar simulator, at 100 mW/cm
2intensity of illumination under the photoelectric conversion efficiency of test battery.Fig. 2 display be the test curve of the current-voltage (I-V) of DSSC.Result shows, the graphene film prepared of the present embodiment to electrode can alternative metals platinum to electrode, battery normally can run and produce photoelectric current and photovoltage.The graphene film prepared in other embodiments of the invention all can use as to electrode, after being packaged into DSSC, can produce effective photoelectric current and photovoltage.
Claims (1)
1. a DSSC is to the preparation method of electrode graphene film, it is characterized in that: (1) first adopts Hummers method to prepare graphite oxide, centrifugation gained graphite oxide also uses deionized water cyclic washing, obtains the graphite oxide aqueous solution that concentration is 5 mg/mL; (2) in the graphite oxide aqueous solution, the N that volumn concentration is 0.5% is added, dinethylformamide (DMF) solution is as dispersant, and utilize ultrasonic stripping method to obtain stably dispersing and the less graphene oxide water solution of the number of plies, the power of ultrasonic oscillator is 800W, and hyperacoustic frequency is 10 kHz; (3) regulate spray gun bore to be 0.4 mm, flow velocity is 3 mL/min, and utilizing spray-on process graphene oxide water solution to be deposited directly to preheat temperature is that in the ITO electro-conductive glass substrate of 300 DEG C, spray time is 30 s, obtains graphene oxide film; (4) baking oven graphene oxide film being placed in 25 DEG C is dried; then hydrazine steam electronation 12 h is put into; and then be slowly be warming up to 500 DEG C in the mixed gas protected high temperature furnace of hydrogen/argon gas of 9 in percent by volume; slowly be down to room temperature after being incubated 1 h, obtaining thickness is that the DSSC of 150 nm is to electrode graphene film.
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| CN104425135B (en) * | 2013-09-05 | 2017-08-29 | 国家纳米科学中心 | Preparation method and applications of the redox graphene to electrode |
| CN103466612A (en) * | 2013-10-08 | 2013-12-25 | 东南大学 | Method for preparing native grapheme by means of frequency mixing ultrasound |
| CN103985546A (en) * | 2014-05-19 | 2014-08-13 | 东南大学 | Graphene-CoS nanosheet composite counter electrode and preparation method thereof |
| CN104591164B (en) * | 2014-12-30 | 2016-09-07 | 常州碳星科技有限公司 | A kind of preparation method of Graphene microbody |
| CN104609409B (en) * | 2015-01-22 | 2016-11-16 | 东南大学 | A kind of preparation method of Graphene millimeter sheet |
| CN106252080B (en) * | 2016-07-29 | 2019-03-12 | 太原理工大学 | A kind of carbon nanomaterial is prepared into dye-sensitized solar cells to the method for electrode |
| CN106409935B (en) * | 2016-10-19 | 2017-10-24 | 华中科技大学 | A kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method thereof |
| CN106807601A (en) * | 2017-03-13 | 2017-06-09 | 中国科学院海洋研究所 | A kind of method for preparing semiconductor powder film photoelectric electrode |
| CN107603225B (en) * | 2017-10-27 | 2018-11-06 | 泉州嘉德利电子材料有限公司 | A kind of the graphene anti-corrosion film and preparation method of Pasting |
| CN108172405B (en) * | 2018-01-09 | 2019-09-03 | 阜阳师范学院 | The quasi-solid-state dye sensitized solar cell prepared using electrochemical reduction oxidation graphene |
| CN108275673A (en) * | 2018-04-07 | 2018-07-13 | 蒋黎婷 | A kind of preparation method of high-performance porous graphene film |
| CN112723344A (en) * | 2020-12-31 | 2021-04-30 | 深圳市华力鸿生物医药科技有限公司 | Preparation method of graphene film |
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| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
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| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
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