CN102129915B - Method for preparing transparent polyaniline electrode in dye-sensitized solar cell - Google Patents
Method for preparing transparent polyaniline electrode in dye-sensitized solar cell Download PDFInfo
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- CN102129915B CN102129915B CN2011100078623A CN201110007862A CN102129915B CN 102129915 B CN102129915 B CN 102129915B CN 2011100078623 A CN2011100078623 A CN 2011100078623A CN 201110007862 A CN201110007862 A CN 201110007862A CN 102129915 B CN102129915 B CN 102129915B
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- Y02E10/542—Dye sensitized solar cells
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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
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a method for preparing a transparent polyaniline electrode in a dye-sensitized solar cell, which comprises the following steps of: preparing aqueous solution of aniline monomers and protonic acid; adding an oxidant into the solution; immersing a cleaned conductive substrate into the solution, performing a reaction for 1 hour to 10 hours at the temperature of 0 to 25 DEG C, then taking the conductive substrate out and cleaning the conductive substrate with de-ionized water; and drying the conductive substrate. The method has the advantages of simplicity of operation, low cost, convenience for scale-up production, and the like. A prepared polyaniline film has high transmission of light, high electrical conductivity and equivalent catalytic performance to platinum and can be used for preparing the transparent dye-sensitized solar cells which allows light to enter from front and back sides at low cost and with high conversion efficiency.
Description
Technical field
The present invention relates to the preparation method of transparent polyaniline electrode in a kind of DSSC, belong to technical field of electronic materials.
Background technology
DSSC (DSSC) is a photoelectrochemical cell of new generation, has with low costly, and preparation is simple, and advantages of environment protection has a good application prospect.Common this battery is made up of electrode three parts the light anode, electrolyte and the platinum that adhere to dyestuff.Yet because platinum is rare noble metal, hindered the large-scale application of DSSC, therefore the cheap non-platinum of development a new generation is the inevitable course to electrode.
Generally speaking, present DSSC is according to the light anode with to the light transmission of electrode, can have the front to enter light and the back side and advance light and advance optical mode for two kinds.The former is corresponding to and situation light anode printing opacity light tight to electrode, and the latter is corresponding to electrode transmits light and the lighttight situation of light anode, and also to be that present DSSC is modal advance optical mode for this.If to electrode and light anode while printing opacity, so just can make can the positive perhaps transparent solar cell of reverse side light inlet.As shown in Figure 1.
From practical application, transparent DSSC will have application prospect widely, especially integrate field of solar energy in building, can use its special roof or window to use glass, when being used for generating electricity, also can play decoration function.In addition also can be applied in automobile or other various electronic products as the intelligent glass that the energy is provided.Platinum electrode now commonly used is through one deck platinum preparation of lamination on FTO glass or simple glass basically, if will guarantee that catalytic and electric conductivity that it is high require it that certain thickness is arranged usually, thereby is nontransparent basically.Though can obtain certain light transmission through the thickness that reduces platinum layer, its catalytic and conductivity all will be had a greatly reduced quality.The more carbon-based material of current research requires micron-sized at least thickness especially as if the conduction and the catalytic that will obtain in addition, and therefore more difficulty is made transparent electrode.So seek new transparent efficiently also be the research direction of DSSC application to electrode.
The conducting polymer that with the polyaniline is representative has good electrical conductivity, catalytic, stability and low cost, is easy to advantages such as preparation, and its application in dye-sensitized solar cells has caused increasing concern.The document of report just at present, have three kinds of methods be used to make polyaniline to electrode film: polyaniline powder cladding process, electrochemical in-situ polymerization, chemical oxidation situ aggregation method.Do not see the report of making transparent polyaniline electrode of it but up to the present all have.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of transparent polyaniline electrode in a kind of DSSC; By this method system polyaniline electrode is had high light transmission, conductivity and catalytic; Can replace platinum, be used to prepare transparent DSSC.
The preparation method of transparent polyaniline electrode in the DSSC of the present invention comprises following steps:
(1) preparation aniline monomer and proton aqueous acid, wherein the concentration of aniline monomer is 0.02mol/L-0.5mol/L, the concentration of Bronsted acid is 0.1mol/L-2mol/L;
(2) in (1) solution, add oxidant, wherein the molar ratio of oxidant and aniline monomer is 0.25-4;
(3) conductive substrates that cleans up is immersed in (2) solution, reaction 1h-10h takes out conductive substrates then, and uses washed with de-ionized water under 0-25 ℃;
(4) dry conductive substrates and polyaniline film.
As a kind of preferred, also be included in dry the doping again with Bronsted acid p-poly-phenyl amine film before.If used Bronsted acid is identical with the middle Bronsted acid of step (1), then directly mix again with Bronsted acid; If different, then earlier use WITH AMMONIA TREATMENT, carry out doping treatment with Bronsted acid again.Because the polyaniline of eigenstate almost is nonconducting, must carries out protonic acid doping to it and could obtain corresponding electric conductivity to satisfy various application demands.If in the preparation process of above-mentioned polyaniline film the reaction time shorter, its doping is not enough so, so must mix again.Or be to use other protonic acid dopings instead, also will mix again in such cases to regulate and control its performance.Be embodied as: the former only needs to get final product in 5-12 hour in the Bronsted acid solution of the same race of polyaniline film immersion 0.1-1 mol/L in will (3).The latter needs earlier the ammoniacal liquor of polyaniline film in (3) with 0.1 mol/L is gone to mix, and surplus back step is the same.
Above-mentioned Bronsted acid can be in hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, the camphorsulfonic acid one or more, and conductive substrates can be substrate of glass or flexible plastic-substrates.
Above-mentioned oxidant can be hydrogen peroxide solution, potassium peroxydisulfate or ammonium persulfate.
Usefulness of the present invention is:
(1) need not specific condition, equipment, raw material sources are extensive, and are with low cost.
(2) preparation method is simple, and fast, repeatability is high, is suitable for large-scale production.
(3) polyaniline film of gained and substrate adhesion are good, have good electrical conductivity, and light transmission and catalytic performance have suitable conversion efficiency with the battery of its assembling with platinum to electrode, and have the transparency.
Description of drawings:
Fig. 1 is the two-sided sketch map that advances the light solar cell according to the invention.
Wherein 1,2,3,4 are respectively: polyaniline is transparent in electrode, electrolyte, TiO
2Film, FTO glass.
Solar cell and the IV performance comparison figure of Pt that Fig. 2 is assembled into for instance of the present invention 5 and instance 6 to the battery of electrode composition.
Embodiment
Below come more detailed explanation the present invention through some embodiments, but the present invention is not limited to these embodiment.
Embodiment 1:
The 25mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 0.1mol/L; And then the ammonium persulfate of adding 1.25mmol; After waiting to stir the FTO glass of cleaning is immersed wherein; At room temperature leave standstill after 10 hours FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 2:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 2mol/L; And then the ammonium persulfate of adding 5mmol; After waiting to stir the FTO glass of cleaning is immersed wherein, at room temperature leave standstill after 10 hours FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 3:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 0.5mol/L; And then the ammonium persulfate of adding 10mmol; After waiting to stir the FTO glass of cleaning is immersed wherein; Under ice-water bath, leave standstill after 5 hours FTO glass is taken out, mix again with the hydrochloric acid of 1mol/L then, take out after about 4 hours and dry down at 120 ℃ with the deionized water clean surface.
Embodiment 4:
The 1mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 2mol/L; And then the ammonium persulfate of adding 4mmol; After waiting to stir the FTO glass of cleaning is immersed wherein, at room temperature leave standstill after 10 hours FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 5:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 1mol/L; And then the ammonium persulfate of adding 10mmol; After waiting to stir the FTO glass of cleaning is immersed wherein, at room temperature leave standstill after 1 hour FTO glass is taken out, use the deionized water clean surface; Then it is inserted in the 1mol/L hydrochloric acid and mix again, take out after about 4 hours and clean and dry down at 120 ℃.
Embodiment 6:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 1mol/L; And then the ammonium persulfate of adding 10mmol; After waiting to stir the FTO glass of cleaning is immersed wherein, at room temperature leave standstill after 1 hour FTO glass is taken out, use the deionized water clean surface; Then it is inserted in the camphorsulfonic acid of 1mol/L and carry out secondary doping, take out after about 4 hours and clean and 120 ℃ of oven dry down.
Embodiment 7:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 0.1mol/L; And then the ammonium persulfate of adding 10mmol; After waiting to stir the ITO/PET (PETG) that cleans is immersed wherein; After leaving standstill 10 hours under 25 ℃, ITO/PET is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 8:
The 10mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 0.1mol/L; And then the ammonium persulfate of adding 10mmol; After waiting to stir the ITO/PEN (PEN) that cleans is immersed wherein; After leaving standstill 10 hours under 4 ℃, ITO/PEN is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 9:
The 25mmol aniline monomer is dissolved in the hydrochloric acid solution of 50ml 0.1mol/L; And then the hydrogen peroxide solution of adding 6mmol; After waiting to stir the ITO/PET that cleans is immersed wherein, after leaving standstill 10 hours under 25 ℃, ITO/PET is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 10:
The 25mmol aniline monomer is dissolved in the sulfuric acid solution of 50ml 0.1mol/L; And then the potassium peroxydisulfate of adding 100mmol; After waiting to stir the FTO glass of cleaning is immersed wherein; At room temperature leave standstill after 10 hours FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 11:
The 25mmol aniline monomer is dissolved in the phosphoric acid solution of 50ml 0.1mol/L; And then the ammonium persulfate of adding 25mmol; After waiting to stir the FTO glass of cleaning is immersed wherein, after leaving standstill 10 hours under 4 ℃, FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Embodiment 12:
The 25mmol aniline monomer is dissolved in the perchloric acid solution of 50ml 0.1mol/L; And then the potassium peroxydisulfate of adding 25mmol; After waiting to stir the FTO glass of cleaning is immersed wherein; At room temperature leave standstill after 10 hours FTO glass is taken out, with the deionized water clean surface and 120 ℃ of oven dry down.
Transparent polyaniline in the above-mentioned instance 5,6 is assembled into the DSSC test performance to electrode and with platinum electrode is compared, and the result is as shown in Figure 2.
Described dye-sensitized solar cell anode is the thick porous TiO of about 8um
2Film, dyestuff are N3 (two (N, N'-2,2'-bipyridine-4, the 4'-dioctyl phthalate) rutheniums of CIS-two thiocyano-s), and electrolytical component is: 0.1mol/L LiI, 0.05mol/L I
2, 0.6mol/L PMII (1-methyl-3-propyl imidazole iodine), 0.5mol/L TBP (tetra-tert pyridine), solvent: propene carbonate and acetonitrile (1/1, vol/vol).
Test condition is the AM1.5G analog light source, and intensity is 100mW/cm
2, the battery effective area is 0.25cm
2
Test result such as following table:
| Electrode type | Open circuit voltage (mV) | Short circuit current (mA/cm2) | Fill factor, curve factor | Conversion efficiency (%) |
| Pt | 650 | 14.4 | 0.6 | 5.60 |
| Instance 5, light is advanced in the front | 720 | 7.63 | 0.624 | 3.43 |
| Instance 5, light is advanced at the back side | 700 | 12.9 | 0.57 | 5.18 |
| Instance 6, light is advanced in the front | 688 | 8.63 | 0.653 | 3.88 |
| Instance 6, light is advanced at the back side | 694 | 13.5 | 0.6 | 5.59 |
Claims (4)
1. the preparation method of transparent polyaniline electrode in the DSSC is characterized in that, comprises following steps:
(1) preparation aniline monomer and proton aqueous acid, wherein the concentration of aniline monomer is 0.02mol/L-0.5mol/L, the concentration of Bronsted acid is 0.1mol/L-2mol/L;
(2) in (1) solution, add oxidant, wherein the molar ratio of oxidant and aniline monomer is 0.25-4;
(3) conductive substrates that cleans up is immersed in (2) solution, in 0-25 ℃ temperature, react 1h-10h, take out conductive substrates then, and use washed with de-ionized water;
(4) dry conductive substrates and polyaniline film;
Also be included in dry the doping again with Bronsted acid p-poly-phenyl amine film before.
2. preparation method as claimed in claim 1 is characterized in that: described Bronsted acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, the camphorsulfonic acid.
3. according to claim 1 or claim 2 preparation method, it is characterized in that: described conductive substrates is substrate of glass or flexible plastic-substrates.
4. according to claim 1 or claim 2 preparation method, it is characterized in that: described oxidant is hydrogen peroxide solution, potassium peroxydisulfate or ammonium persulfate.
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| CN103059294B (en) * | 2013-01-21 | 2015-05-13 | 潍柴动力股份有限公司 | Synthetic method of electrode material polyaniline |
| CN103151172A (en) * | 2013-03-07 | 2013-06-12 | 复旦大学 | Preparation method of polyaniline nanowire array counter electrode of dye-sensitized solar cell |
| CN103966583B (en) * | 2014-05-07 | 2016-08-17 | 哈尔滨工业大学 | A kind of preparation method of flexible gold thin film surface electrochromic polyanilines thin film |
| CN106935414B (en) * | 2017-04-24 | 2019-04-02 | 福州大学 | A kind of cross linked porous polyaniline electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680464A (en) * | 2004-03-22 | 2005-10-12 | 尹虎声 | Polyaniline having high electrical conductivity and producing process thereof |
| CN101302340A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite body, conductive polymer composition and electronic component using the conductive polymer composition |
| CN101565544A (en) * | 2009-05-05 | 2009-10-28 | 北京化工大学 | Nano composite material of polyaniline intercalation titanate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680464A (en) * | 2004-03-22 | 2005-10-12 | 尹虎声 | Polyaniline having high electrical conductivity and producing process thereof |
| CN101302340A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite body, conductive polymer composition and electronic component using the conductive polymer composition |
| CN101565544A (en) * | 2009-05-05 | 2009-10-28 | 北京化工大学 | Nano composite material of polyaniline intercalation titanate and preparation method thereof |
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