CN108172401A - Dye-sensitized cell combined counter electrode and its preparation method and application - Google Patents
Dye-sensitized cell combined counter electrode and its preparation method and application Download PDFInfo
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- CN108172401A CN108172401A CN201711448716.8A CN201711448716A CN108172401A CN 108172401 A CN108172401 A CN 108172401A CN 201711448716 A CN201711448716 A CN 201711448716A CN 108172401 A CN108172401 A CN 108172401A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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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 present invention discloses a kind of dye-sensitized cell combined counter electrode and its preparation method and application, mass fraction including conductive substrates and the nano platinum particle being sequentially coated in the conductive substrates is the titanium dioxide reflecting layer that 10~35% graphene/platinum composite bed and the nano-titanium dioxide composite mortar by containing titania-doped microballoon are formed.Compared with prior art, nano platinum particle is supported on graphene film in the graphene/platinum composite bed that dye-sensitized cell of the invention is coated with combined counter electrode, both ensure that electrode for I‑/I3 ‑The catalytic performance of redox couple in turn ensures the electric conductivity to electrode, improves corrosion resistance, can also substantially reduce cost, improves catalytic efficiency；Titanium dioxide reflecting layer effectively will can not reflect back into light anode by the sunlight that light anode absorbs and carry out double absorption, so as to improve the utilization rate of sunlight, the photoelectric conversion efficiency of battery is further improved, it is simple for process, yield is high, has broad application prospects.
Description
Technical field
The present invention relates to technical field of solar batteries, more particularly to a kind of dye-sensitized cell combined counter electrode and its
Preparation method and application.
Background technology
With becoming increasingly conspicuous for shortage of resources and problem of environmental pollution, solar energy is more next as a kind of clean reproducible energy
More paid close attention to by common people.Currently, by solar cell carry out opto-electronic conversion be human use's solar energy main path it
One.In solar cells, silicon solar cell occupies part of solar cell 90% because of its conversion ratio height and technology maturation
Volume, however silicon systems solar cell, because of its complex process, expensive, material requirements is harsh and is difficult to popularize.How to improve too
The photoelectric conversion efficiency of positive energy battery simultaneously effectively reduces its manufacture cost, becomes many solar cell working persons and constantly pursues
Target.
Dye-sensitized solar cells (DSSC) are to imitate the novel solar battery developed of photosynthesis, have it is low into
Originally, the advantages that easily fabricated and high efficiency, it is most likely that substitution conventional solid-state photovoltaic device, such as silicon solar cell, cadmium antimonide
Hull cell and copper indium gallium selenide film battery etc. become the leading of following solar cell.DSSC is mainly catalyzed by dye sensitization
I3Porous semi-conductor nano-crystal film, contain I-/I3The electrolyte of oxidation-reduction pair and to electrode form, wherein, to electricity
The main function of pole is：Electronics is collected and transported, that is, receive the electronics of battery external loop and passes it on the oxygen in electrolyte
Change reduction reaction electronics pair；It adsorbs and is catalyzed I3-；Reflectance-transmittance light.Therefore, there is good electric conductivity and high catalytic activity
It plays an important role to electrode to the photoelectric properties and photoelectric conversion efficiency that improve DSSC.At present generally with transparent conductive film
Glass on plate metal platinum and be used as to electrode, still, the use of noble metal platinum not only with dye-sensitized solar cells it is low into
This original intention is disagreed, hence it is evident that limits to its large-scale production and application, and there is the phenomenon that being corroded from an electrolyte, can lead to device
Part stability declines.Therefore, the research hotspot that novel cheap non-platinum is DSSC fields to electrode is explored.
Invention content
For solution more than technical problem, the present invention provides a kind of dye-sensitized cell combined counter electrode and preparation method thereof
And application, existing Pt electrodes are expensive to cause solar cell of high cost to solve, also with electrolyte-resistant corrosivity and compared with
Polyelectrolyte catalytic activity, the problem of improving the stability and the market competitiveness of dye-sensitized solar cells.
The technical solution adopted by the present invention is as follows：A kind of dye-sensitized cell combined counter electrode, key are：Including leading
Electric substrate and the graphene/platinum composite bed being sequentially coated in the conductive substrates and titanium dioxide reflecting layer；
The mass fraction of nano platinum particle is 10~35% in the graphene/platinum composite bed；
The titanium dioxide reflecting layer is made of the nano-titanium dioxide composite mortar for containing titania-doped microballoon.
Preferably, the conductive substrates are FTO electro-conductive glass or ITO electro-conductive glass.
A kind of preparation method of dye-sensitized cell combined counter electrode, key are to include the following steps：
Step 1: the preparation of graphene/platinum compound：It is 1 by mass ratio:The graphene oxide and chloroplatinic acid of (0.5~4)
Ultrasonic disperse is carried out after aqueous solution mixing, mass concentration is then slowly added dropwise while stirring as 0.5~3mol/L sodium borohydride water
Solution, after being stirred to react 2~4h, by reactant by being centrifugally separating to obtain graphene/platinum compound；
Step 2: the preparation of titanium dioxide composite mortar：It is 1 by mass ratio：(5~8)：The titanium dioxide of (1~3) is micro-
Ball, nano-titania particle and Zirconia particles are added in absolute ethyl alcohol, and after ultrasonic vibration, it is fine then to add ethyl
The ethanol solution and terpinol of element are tieed up, after again passing by supersound process, evaporation absolute ethyl alcohol obtains titanium dioxide composite pulp
Material；
Step 3: the preparation of combined counter electrode：Graphene/platinum compound made from step 1 is added to absolute ethyl alcohol
In, graphene/platinum dispersion liquid is obtained after supersound process, by graphene/platinum dispersion in conductive substrates, at 60 DEG C
The graphene/platinum composite bed is formed after lower vacuum drying 2h, titanium dioxide composite mortar made from step 2 is coated in institute
It states on graphene/platinum composite bed, is dried at 60~85 DEG C, it is anti-finally to form the titanium dioxide after 400~500 DEG C of sintering
Layer is penetrated, obtains combined counter electrode.
Preferably, graphene oxide described in the step 1 is made by following steps：9~15ml concentrated sulfuric acids are heated to
75~85 DEG C, 1.6g potassium persulfates and 1.6g phosphorus pentoxides are added in, stirring is until all dissolvings；Then add in 1.8~
2.2g graphite, reacts 4~5h at a temperature of 75~85 DEG C, and filtering, washing obtain expanded graphite；Expanded graphite is added to
Ice bath cooling 75~85ml concentrated sulfuric acids in, under magnetic stirring into this mixture under be slowly added to 8~12g potassium permanganate,
Then 3~5h is reacted at 30~40 DEG C, reacts 1.5~2.5h again at room temperature；The deionized water of 150~170ml is slowly added to,
Temperature is kept to be no more than 50 DEG C, continues 1.5~2.5h of stirring；Add 450~490ml water and 30wt% hydrogen peroxide 8~
12ml generates the solution of glassy yellow, after this solution is placed for 24 hours, outwells supernatant, and remaining liquid is first then used 3wt% sulphur
Acid and 1wt% hydrogenperoxide steam generators are washed twice respectively, then wash twice with 10wt%HCl again, finally dialysis 6~8 in water
My god, obtained solid is dry at 45~55 DEG C, and graphite oxide is made；Graphite oxide is placed in deionized water, graphite oxide
Mass ratio with deionized water is (0.3~0.5)：1, it is dissociated through 10~30min of ul-trasonic irradiation, ultrasonic power 150W
To graphene oxide solution.
Preferably, titanium dioxide microballoon sphere described in the step 2 is made by following steps：By a concentration of 10~30%
Titanium trichloride dilute hydrochloric acid solution, glacial acetic acid are 1 by volume with absolute ethyl alcohol: (1.5~3): (25~35) mix, and obtain solution
Mass concentration is that the polyethylene glycol of a concentration of 0.6~1.5mmol/L, urea are added in solution A by A, polyethylene glycol and urea
Weight ratio be 0.5~1.5, stir 10~50min after be transferred in high-pressure reaction vessel, at 100~200 DEG C react 10~
15h centrifuges products therefrom, washs after drying 1~4h at 40~100 DEG C, obtains titanium dioxide microballoon sphere.
Preferably, the ratio of titanium dioxide microballoon sphere and absolute ethyl alcohol is (0.5~1.5) g: (3~10) in the step 2
ml；The weight ratio of ethyl cellulose and terpinol is (0.05~0.15)：1, the weight of ethyl cellulose and titanium dioxide microballoon sphere
Than for (0.1~0.5)：1.
Preferably, graphene/platinum composite bed described in step 3 by three layers of graphene/platinum composite coated described
It is formed in conductive substrates, the thickness of the graphene/platinum composite bed is 12~20 μm.
Preferably, titanium dioxide reflecting layer described in step 3 is coated in described by two layers of titanium dioxide composite mortar
It is formed on graphene/platinum composite bed, the thickness in the titanium dioxide reflecting layer is 8~15 μm.
A kind of method for being prepared dye-sensitized cell with combined counter electrode using dye-sensitized cell, key are：By institute
Dye-sensitized cell combined counter electrode is stated to be packaged and then in the dye-sensitized cell combined counter electrode with light anode
Electrolyte is injected between light anode, that is, is assembled into dye-sensitized cell.
Preferably, light anode is to adsorb the titanium dioxide electrodes of N719 dyestuffs；The electrolyte be comprising 0.2M1- propyl-
3- methylpyridinium iodides imidazoles, 0.05M iodine, 0.1M lithium iodides, the acetonitrile of 0.2M tetrabutylammonium iodides and 0.5M4- tert .-butylpyridines are molten
Liquid.
Advantageous effect：Compared with prior art, the present invention provides a kind of dye-sensitized cell combined counter electrode and its
Preparation method and application, nano platinum particle is supported on graphene film in the graphene/platinum composite bed of coating, both ensure that electricity
Pole is for I-/I3The catalytic performance of redox couple in turn ensures the electric conductivity to electrode, improves corrosion resistance, can also be big
The big usage amount for reducing valuable catalyst so as to reduce cost, improves catalytic efficiency；Titanium dioxide is micro- in titanium dioxide reflecting layer
Ball has the specific surface area and light scattering property of bigger, then will effectively can not reflected back by the sunlight that light anode absorbs
Light anode simultaneously carries out double absorption, so as to improve the utilization rate of sunlight, further improves the photoelectric conversion efficiency of battery, work
Skill is simple, and yield is high, has broad application prospects.
Description of the drawings
Fig. 1 is titanium dioxide microballoon sphere scanning electron microscope diagram；
Fig. 2 is cyclic voltammetry curve graphs of the combined counter electrode I-III with platinum to electrode, and wherein curve 11-13 distinguishes
For the I-V curve of combined counter electrode I-III, curve 14 is Pt to the I-V curve of electrode；
Fig. 3 is the cyclic voltammetry curve of combined counter electrode III continuous scannings 200 times.
Specific embodiment
For those skilled in the art is made to be better understood from technical scheme of the present invention, With reference to embodiment to this
Invention elaborates.
The preparation of 1 dye-sensitized cell of embodiment combined counter electrode I
Step 1: the preparation of graphene/platinum compound：9~15ml concentrated sulfuric acids are heated to 75~85 DEG C, add in 1.6g mistakes
Two potassium sulfates and 1.6g phosphorus pentoxides, stirring is until all dissolvings；Then 1.8~2.2g graphite is added in, in 75~85 DEG C of temperature
Degree 4~5h of lower reaction, filtering, washing obtain expanded graphite；Expanded graphite is added to the dense sulphur of 75~85ml cooled down in ice bath
In acid, under magnetic stirring into this mixture under be slowly added to 8~12g potassium permanganate, then at 30~40 DEG C reaction 3~
5h reacts 1.5~2.5h again at room temperature；The deionized water of 150~170ml is slowly added to, temperature is kept to be no more than 50 DEG C, is continued
Stir 1.5~2.5h；The water of 450~490ml and 30wt% 8~12ml of hydrogen peroxide are added, generates the solution of glassy yellow, this is molten
After liquid is placed for 24 hours, supernatant is outwelled, then first washes remaining liquid respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generators
It twice, is then washed twice with 10wt%HCl again, finally dialysis 6~8 days, obtained solid are done at 45~55 DEG C in water
It is dry, graphite oxide is made；Graphite oxide is placed in deionized water, the mass ratio of graphite oxide and deionized water for (0.3~
0.5)：1, through 10~30min of ul-trasonic irradiation, ultrasonic power 150W, dissociation obtains graphene oxide solution；Then by quality
Than being 1：Ultrasonic disperse is carried out after 0.5 graphene oxide solution and chloroplatinic acid aqueous solution mixing, is then slowly dripped while stirring
Add mass concentration for 0.5~3mol/L sodium borohydride aqueous solutions, after being stirred to react 2~4h, by reactant by centrifuging
To graphene/platinum compound, the mass fraction of nano platinum particle is 10% in the graphene/platinum composite bed；
Step 2: the preparation of titanium dioxide composite mortar：By a concentration of 10~30% titanium trichloride dilute hydrochloric acid solution, ice
Acetic acid is 1 by volume with absolute ethyl alcohol: mass concentration is a concentration of by (1.5~3): (25~35) mix, and obtain solution A
Polyethylene glycol, the urea of 0.6~1.5mmol/L is added in solution A, and the weight ratio of polyethylene glycol and urea is 0.5~1.5, is stirred
It is transferred in high-pressure reaction vessel after mixing 10~50min, 10~15h is reacted at 100~200 DEG C, by products therefrom centrifugation point
From, wash after at 40~100 DEG C dry 1~4h, obtain titanium dioxide microballoon sphere；Then it is 1 by mass ratio：5：1 titanium dioxide
Titanium microballoon, nano-titania particle and Zirconia particles are added in absolute ethyl alcohol, wherein titanium dioxide microballoon sphere and anhydrous second
The ratio of alcohol is 0.5g: 3ml；After ultrasonic vibration, the ethanol solution and terpinol of ethyl cellulose are then added,
The weight ratio of middle ethyl cellulose and terpinol is 0.05：1, the weight ratio of ethyl cellulose and titanium dioxide microballoon sphere is 0.1：1,
After again passing by supersound process, evaporation absolute ethyl alcohol obtains titanium dioxide composite mortar；
Step 3: the preparation of combined counter electrode：Graphene/platinum compound made from step 1 is added to absolute ethyl alcohol
In, graphene/platinum dispersion liquid is obtained after supersound process, by graphene/platinum dispersion on FTO electro-conductive glass,
The graphene/platinum composite bed is formed after being dried in vacuo 2h at 60 DEG C, and repetitive coatings-drying process, the graphene/platinum is compound
Layer is formed by three layers of graphene/platinum composite coated on the FTO electro-conductive glass or ITO electro-conductive glass, the graphite
The thickness of alkene/platinum composite bed is 12~20 μm, and titanium dioxide composite mortar made from step 2 is coated in the graphene/platinum
It on composite bed, is dried at 60~85 DEG C, the titanium dioxide reflecting layer is finally formed after 400~500 DEG C of sintering, repeat to apply
- sintering process is covered-dries, the titanium dioxide reflecting layer is coated in the graphite by two layers of titanium dioxide composite mortar
It is formed on alkene/platinum composite bed, the thickness in the titanium dioxide reflecting layer is 8~15 μm, obtains dye-sensitized cell with compound right
Electrode I.
The preparation of 2 dye-sensitized cell of embodiment combined counter electrode II
Step 1: the preparation of graphene/platinum compound：9~15ml concentrated sulfuric acids are heated to 75~85 DEG C, add in 1.6g mistakes
Two potassium sulfates and 1.6g phosphorus pentoxides, stirring is until all dissolvings；Then 1.8~2.2g graphite is added in, in 75~85 DEG C of temperature
Degree 4~5h of lower reaction, filtering, washing obtain expanded graphite；Expanded graphite is added to the dense sulphur of 75~85ml cooled down in ice bath
In acid, under magnetic stirring into this mixture under be slowly added to 8~12g potassium permanganate, then at 30~40 DEG C reaction 3~
5h reacts 1.5~2.5h again at room temperature；The deionized water of 150~170ml is slowly added to, temperature is kept to be no more than 50 DEG C, is continued
Stir 1.5~2.5h；The water of 450~490ml and 30wt% 8~12ml of hydrogen peroxide are added, generates the solution of glassy yellow, this is molten
After liquid is placed for 24 hours, supernatant is outwelled, then first washes remaining liquid respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generators
It twice, is then washed twice with 10wt%HCl again, finally dialysis 6~8 days, obtained solid are done at 45~55 DEG C in water
It is dry, graphite oxide is made；Graphite oxide is placed in deionized water, the mass ratio of graphite oxide and deionized water for (0.3~
0.5)：1, through 10~30min of ul-trasonic irradiation, ultrasonic power 150W, dissociation obtains graphene oxide solution；Then by quality
Than being 1：Ultrasonic disperse is carried out after 4 graphene oxide solution and chloroplatinic acid aqueous solution mixing, is then slowly added dropwise while stirring
Mass concentration is 0.5~3mol/L sodium borohydride aqueous solutions, after being stirred to react 2~4h, by reactant by being centrifugally separating to obtain
Graphene/platinum compound, the mass fraction of nano platinum particle is 35% in the graphene/platinum composite bed；
Step 2: the preparation of titanium dioxide composite mortar：By a concentration of 10~30% titanium trichloride dilute hydrochloric acid solution, ice
Acetic acid is 1 by volume with absolute ethyl alcohol: mass concentration is a concentration of by (1.5~3): (25~35) mix, and obtain solution A
Polyethylene glycol, the urea of 0.6~1.5mmol/L is added in solution A, and the weight ratio of polyethylene glycol and urea is 0.5~1.5, is stirred
It is transferred in high-pressure reaction vessel after mixing 10~50min, 10~15h is reacted at 100~200 DEG C, by products therefrom centrifugation point
From, wash after at 40~100 DEG C dry 1~4h, obtain titanium dioxide microballoon sphere；Then it is 1 by mass ratio：8：3 titanium dioxide
Titanium microballoon, nano-titania particle and Zirconia particles are added in absolute ethyl alcohol, wherein titanium dioxide microballoon sphere and anhydrous second
The ratio of alcohol is 1.5g: 10ml；After ultrasonic vibration, the ethanol solution and terpinol of ethyl cellulose are then added,
Wherein the weight ratio of ethyl cellulose and terpinol is 0.15：1, the weight ratio of ethyl cellulose and titanium dioxide microballoon sphere is 0.5：
1, after again passing by supersound process, evaporation absolute ethyl alcohol obtains titanium dioxide composite mortar；
Step 3: the preparation of combined counter electrode：Graphene/platinum compound made from step 1 is added to absolute ethyl alcohol
In, graphene/platinum dispersion liquid is obtained after supersound process, by graphene/platinum dispersion on ITO electro-conductive glass,
The graphene/platinum composite bed is formed after being dried in vacuo 2h at 60 DEG C, and repetitive coatings-drying process, the graphene/platinum is compound
Layer is formed by three layers of graphene/platinum composite coated on the ITO electro-conductive glass, the graphene/platinum composite bed
Thickness is 12~20 μm, titanium dioxide composite mortar made from step 2 is coated on the graphene/platinum composite bed, 60
It is dried at~85 DEG C, finally forms the titanium dioxide reflecting layer, repetitive coatings-drying-sintering after 400~500 DEG C of sintering
Process, the titanium dioxide reflecting layer are coated in by two layers of titanium dioxide composite mortar on the graphene/platinum composite bed
It forms, the thickness in the titanium dioxide reflecting layer is 8~15 μm, obtains dye-sensitized cell combined counter electrode II.
The preparation of 3 dye-sensitized cell of embodiment combined counter electrode III
Step 1: the preparation of graphene/platinum compound：9~15ml concentrated sulfuric acids are heated to 75~85 DEG C, add in 1.6g mistakes
Two potassium sulfates and 1.6g phosphorus pentoxides, stirring is until all dissolvings；Then 1.8~2.2g graphite is added in, in 75~85 DEG C of temperature
Degree 4~5h of lower reaction, filtering, washing obtain expanded graphite；Expanded graphite is added to the dense sulphur of 75~85ml cooled down in ice bath
In acid, under magnetic stirring into this mixture under be slowly added to 8~12g potassium permanganate, then at 30~40 DEG C reaction 3~
5h reacts 1.5~2.5h again at room temperature；The deionized water of 150~170ml is slowly added to, temperature is kept to be no more than 50 DEG C, is continued
Stir 1.5~2.5h；The water of 450~490ml and 30wt% 8~12ml of hydrogen peroxide are added, generates the solution of glassy yellow, this is molten
After liquid is placed for 24 hours, supernatant is outwelled, then first washes remaining liquid respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generators
It twice, is then washed twice with 10wt%HCl again, finally dialysis 6~8 days, obtained solid are done at 45~55 DEG C in water
It is dry, graphite oxide is made；Graphite oxide is placed in deionized water, the mass ratio of graphite oxide and deionized water for (0.3~
0.5)：1, through 10~30min of ul-trasonic irradiation, ultrasonic power 150W, dissociation obtains graphene oxide solution；Then by quality
Than being 1：Ultrasonic disperse is carried out after 2 graphene oxide solution and chloroplatinic acid aqueous solution mixing, is then slowly added dropwise while stirring
Mass concentration is 0.5~3mol/L sodium borohydride aqueous solutions, after being stirred to react 2~4h, by reactant by being centrifugally separating to obtain
Graphene/platinum compound, the mass fraction of nano platinum particle is 15% in the graphene/platinum composite bed；
Step 2: the preparation of titanium dioxide composite mortar：By a concentration of 10~30% titanium trichloride dilute hydrochloric acid solution, ice
Acetic acid is 1 by volume with absolute ethyl alcohol: mass concentration is a concentration of by (1.5~3): (25~35) mix, and obtain solution A
Polyethylene glycol, the urea of 0.6~1.5mmol/L is added in solution A, and the weight ratio of polyethylene glycol and urea is 0.5~1.5, is stirred
It is transferred in high-pressure reaction vessel after mixing 10~50min, 10~15h is reacted at 100~200 DEG C, by products therefrom centrifugation point
From, wash after at 40~100 DEG C dry 1~4h, obtain titanium dioxide microballoon sphere；Then it is 1 by mass ratio：6：2 titanium dioxide
Titanium microballoon, nano-titania particle and Zirconia particles are added in absolute ethyl alcohol, wherein titanium dioxide microballoon sphere and anhydrous second
The ratio of alcohol is 1g: 8ml；After ultrasonic vibration, the ethanol solution and terpinol of ethyl cellulose are then added, wherein
The weight ratio of ethyl cellulose and terpinol is 0.1：1, the weight ratio of ethyl cellulose and titanium dioxide microballoon sphere is 0.2：1, then
It is secondary after supersound process, evaporation absolute ethyl alcohol obtain titanium dioxide composite mortar；
Step 3: the preparation of combined counter electrode：Graphene/platinum compound made from step 1 is added to absolute ethyl alcohol
In, graphene/platinum dispersion liquid is obtained after supersound process, by graphene/platinum dispersion on FTO electro-conductive glass,
The graphene/platinum composite bed is formed after being dried in vacuo 2h at 60 DEG C, and repetitive coatings-drying process, the graphene/platinum is compound
Layer is formed by three layers of graphene/platinum composite coated on the FTO electro-conductive glass, the graphene/platinum composite bed
Thickness is 12~20 μm, titanium dioxide composite mortar made from step 2 is coated on the graphene/platinum composite bed, 60
It is dried at~85 DEG C, finally forms the titanium dioxide reflecting layer, repetitive coatings-drying-sintering after 400~500 DEG C of sintering
Process, the titanium dioxide reflecting layer are coated in by two layers of titanium dioxide composite mortar on the graphene/platinum composite bed
It forms, the thickness in the titanium dioxide reflecting layer is 8~15 μm, obtains dye-sensitized cell combined counter electrode III.
The preparation of 4 dye-sensitized cell I of embodiment
The FTO TiCl4 of 30mM are handled into 30min in 70 DEG C, after dry, are placed in 450 DEG C of processing 30min in Muffle furnace,
Natural cooling；By TiO2 colloids blade coating on TiCl4 treated FTO electro-conductive glass, 120 DEG C of baking 20min repeat blade coating
Once, and again 20min is toasted in 120 DEG C.In Muffle furnace, 450 DEG C of sintering 30min naturally cool to 70 DEG C, will be calcined
Titanium dioxide photo anode be placed in a concentration of 3 × 10-4The (Yi Jing ︰ tert-butyl alcohols=1 ︰, 1 percents by volume in the solution of M N719),
Under 35 DEG C of constant temperature, 2h is sensitized, the light anode of dye sensitization is taken out, acetonitrile washing and naturally dry, then by light anode
The dye-sensitized cell prepared with embodiment 1 carries out heat-seal with combined counter electrode I with the sealed membrane that thickness is 0.128nm, electricity
Pond effective area is 0.1cm2, electrolyte is then injected into the aperture to electrode with pipettor gun, the electrolyte be comprising
0.2M 1- propyl -3- methylpyridinium iodides imidazoles, 0.05M iodine, 0.1M lithium iodides, 0.2M tetrabutylammonium iodides and 0.5M 4- tertiary butyls
The acetonitrile solution of pyridine, reheating are sealed to the aperture on electrode, both obtain the dye-sensitized solar cells I.
The preparation of 5 dye-sensitized cell II of embodiment
Equipment and operation with embodiment 4, unlike be dye-sensitized cell prepared by embodiment 2 with compound right to electrode
Electrode II, obtained dye-sensitized solar cells II.
The preparation of 6 dye-sensitized cell III of embodiment
Equipment and operation with embodiment 4, unlike be dye-sensitized cell prepared by embodiment 3 with compound right to electrode
Electrode III, obtained dye-sensitized solar cells III.
7 comparative example of embodiment
Equipment and operation with embodiment 4, unlike be platinum standard to electrode, the obtained dye sensitization sun to electrode
It can battery IV.
The dye-sensitized cell that each embodiment is prepared is carried out with combined counter electrode and dye-sensitized solar cells
Following test：
(1) cyclic voltammetry of combined counter electrode
Compare the Cyclic voltamogram of Pt, dye-sensitized cell combined counter electrode I-III using three-electrode system measurement.
Wherein, the use of to electrode, reference electrode is respectively platinized platinum, Ag/Ag-Electrode, working electrode are electrode to be measured.Electrolyte forms：
9mM LiI, 1mM I2, 0.1M LiClO4, solvent is acetonitrile solution；Speed is swept as 0.05VS-1.By comparing oxidationreduction electricity
Shape, position, overpotential size, size of cathodic peak current density of stream peak etc., it is possible to determine that electrode material catalytic activity
Quality.
As shown in Fig. 2, dye-sensitized cell with combined counter electrode I-III to the cyclic voltammetry curve of electrode
(11-13) is similar to the curve of electrode (14) to platinum at potential position in shape, while shows two pairs of oxygen
Change reduction peak, i.e. I-/I3And I3-/I2The reduction peak of the two reduction reactions, this illustrates that it has similar catalysis to platinum electrode
Activity.Dye-sensitized cell is with combined counter electrode I-III for I-/I3The electrochemical catalysis activity of this oxidation-reduction pair
Platinum electrode is apparently higher than, since nano platinum particle is uniformly supported on graphite film, graphite film is provided for nano platinum particle
Support, it is therefore prevented that the polymerization of nano platinum particle so as to provide the specific surface area of bigger conducive to catalysis, is conducive to be assembled into dyestuff
The raising of sensitization solar battery performance,
Fig. 3 shows dye-sensitized cell combined counter electrode III in I3-/I-Scanning is contacted in oxidation-reduction pair system
200 obtained cyclic voltammetry curves.Scanning result shows that redox peaks do not have significant change, shows that dye-sensitized cell is used
Combined counter electrode III has preferable stability.
(2) photoelectric properties of dye-sensitized solar cells
Using 2400 digital sourcemeters of U.S. Keith1ey acquisition photoelectric current, photovoltage, short circuit current (J is obtainedsc), open circuit
Voltage (Voc), fill factor (FF) and photoelectric conversion efficiency, (be in effective illuminating area：0.16cm2, in AM1.5-
100mW/cm2Light intensity under tested), test result is as shown in table 2.
The photoelectric properties test result of 1 each dye-sensitized solar cells DSSC of table
| DSSCI | DSSCII | DSSCIII | DSSCIV | |
| Voc(mV) | 758 | 743 | 778 | 747 |
| Jsc(mA/cm2) | 17.5 | 16.7 | 18.6 | 13.1 |
| FF | 0.63 | 0.62 | 0.67 | 0.66 |
| η (%) | 7.63 | 7.52 | 7.84 | 6.54 |
It is tested from spectrochemical property, electrochemical properties and photoelectric properties, it can be seen that dye-sensitized cell of the invention
With combined counter electrode have high electric conductivity, high specific surface area, thermostabilization and chemical stability it is good, the graphene/platinum of introducing
Composite bed provides big catalysis specific surface, reduces charge migration resistance and redox potential, greatly reduces valuable catalyst
Usage amount, so as to reduce cost；Titanium dioxide reflecting layer will effectively can be then reflected back by the sunlight that light anode absorbs
To light anode and double absorption is carried out, so as to improve the utilization rate of sunlight, further improves the photoelectric conversion efficiency of battery,
Photoelectric conversion efficiency increases 15-20% relative to traditional platinum electrode dye cell.Dye-sensitized cell prepared by the present invention
With combined counter electrode, preparation process is simple, at low cost, catalytic activity is high, has good application prospect.
Finally it is to be appreciated that foregoing description is merely a preferred embodiment of the present invention, those skilled in the art is in the present invention
Enlightenment under, under the premise of without prejudice to present inventive concept and claim, expression, such change as multiple types can be made
It changes and each falls within protection scope of the present invention.
Claims (10)
1. a kind of dye-sensitized cell combined counter electrode, it is characterised in that：Including conductive substrates and it is sequentially coated at described lead
Graphene/platinum composite bed and titanium dioxide reflecting layer in electric substrate；
The mass fraction of nano platinum particle is 10~35% in the graphene/platinum composite bed；
The titanium dioxide reflecting layer is made of the nano-titanium dioxide composite mortar for containing titania-doped microballoon.
2. dye-sensitized cell combined counter electrode according to claim 1, it is characterised in that：The conductive substrates are
FTO electro-conductive glass or ITO electro-conductive glass.
3. a kind of preparation method of the dye-sensitized cell combined counter electrode described in claim 1-2, it is characterised in that including
Following steps：
Step 1: the preparation of graphene/platinum compound：It is 1 by mass ratio:The graphene oxide and chloroplatinic acid of (0.5~4) are water-soluble
Ultrasonic disperse is carried out after liquid mixing, mass concentration is then slowly added dropwise while stirring as 0.5~3mol/L sodium borohydride aqueous solutions,
After being stirred to react 2~4h, by reactant by being centrifugally separating to obtain graphene/platinum compound；
Step 2: the preparation of titanium dioxide composite mortar：It is 1 by mass ratio：(5~8)：The titanium dioxide microballoon sphere of (1~3) is received
Rice TiO 2 particles and Zirconia particles are added in absolute ethyl alcohol, after ultrasonic vibration, then add ethyl cellulose
Ethanol solution and terpinol, after again passing by supersound process, evaporation absolute ethyl alcohol obtain titanium dioxide composite mortar；
Step 3: the preparation of combined counter electrode：Graphene/platinum compound made from step 1 is added in absolute ethyl alcohol, warp
Graphene/platinum dispersion liquid is obtained after crossing supersound process, it is true at 60 DEG C by graphene/platinum dispersion in conductive substrates
The graphene/platinum composite bed is formed after the dry 2h of sky, titanium dioxide composite mortar made from step 2 is coated in the stone
It on black alkene/platinum composite bed, is dried at 60~85 DEG C, the titanium dioxide reflection is finally formed after 400~500 DEG C of sintering
Layer, obtains combined counter electrode.
4. the preparation method of dye-sensitized cell combined counter electrode according to claim 2, it is characterised in that the step
Graphene oxide is made by following steps described in rapid one：9~15ml concentrated sulfuric acids are heated to 75~85 DEG C, 1.6g is added in and crosses two
Potassium sulfate and 1.6g phosphorus pentoxides, stirring is until all dissolvings；Then 1.8~2.2g graphite is added in, in 75~85 DEG C of temperature
4~5h of lower reaction, filtering, washing, obtains expanded graphite；Expanded graphite is added to the 75~85ml concentrated sulfuric acids cooled down in ice bath
In, under magnetic stirring into this mixture under be slowly added to 8~12g potassium permanganate, then at 30~40 DEG C reaction 3~
5h reacts 1.5~2.5h again at room temperature；The deionized water of 150~170ml is slowly added to, temperature is kept to be no more than 50 DEG C, is continued
Stir 1.5~2.5h；The water of 450~490ml and 30wt% 8~12ml of hydrogen peroxide are added, generates the solution of glassy yellow, this is molten
After liquid is placed for 24 hours, supernatant is outwelled, then first washes remaining liquid respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generators
It twice, is then washed twice with 10wt%HCl again, finally dialysis 6~8 days, obtained solid are done at 45~55 DEG C in water
It is dry, graphite oxide is made；Graphite oxide is placed in deionized water, the mass ratio of graphite oxide and deionized water for (0.3~
0.5)：1, through 10~30min of ul-trasonic irradiation, ultrasonic power 150W, dissociation obtains graphene oxide solution.
5. the preparation method of the dye-sensitized cell combined counter electrode according to Claims 2 or 3, it is characterised in that described
Titanium dioxide microballoon sphere described in step 2 is made by following steps：By a concentration of 10~30% titanium trichloride dilute hydrochloric acid solution,
Glacial acetic acid is 1 by volume with absolute ethyl alcohol: mass concentration is concentration by (1.5~3): (25~35) mix, and obtain solution A
Polyethylene glycol, urea for 0.6~1.5mmol/L are added in solution A, and the weight ratio of polyethylene glycol and urea is 0.5~1.5,
It is transferred in high-pressure reaction vessel after 10~50min of stirring, 10~15h is reacted at 100~200 DEG C, products therefrom is centrifuged
Separation washs after drying 1~4h at 40~100 DEG C, obtains titanium dioxide microballoon sphere.
6. the preparation method of dye-sensitized cell combined counter electrode according to claim 4, it is characterised in that：The step
The ratio of titanium dioxide microballoon sphere and absolute ethyl alcohol is (0.5~1.5) g: (3~10) ml in rapid two；Ethyl cellulose and terpinol
Weight ratio be (0.05~0.15)：1, the weight ratio of ethyl cellulose and titanium dioxide microballoon sphere is (0.1~0.5)：1.
7. the preparation method of dye-sensitized cell combined counter electrode according to claim 6, it is characterised in that：Step 3
Described in graphene/platinum composite bed formed in the conductive substrates by three layers of graphene/platinum composite coated, the stone
The thickness of black alkene/platinum composite bed is 12~20 μm.
8. the preparation method of the dye-sensitized cell combined counter electrode described according to claim 6 or 7, it is characterised in that：Step
Titanium dioxide reflecting layer described in rapid three is coated in by two layers of titanium dioxide composite mortar on the graphene/platinum composite bed
It forms, the thickness in the titanium dioxide reflecting layer is 8~15 μm.
9. a kind of dye-sensitized cell using described in claims 1 or 22 prepares the side of dye-sensitized cell with combined counter electrode
Method, it is characterised in that：The dye-sensitized cell is packaged with combined counter electrode with light anode and then quick in the dyestuff
Electrochemical cell is assembled into dye-sensitized cell with electrolyte is injected between combined counter electrode and light anode.
10. the method that dye-sensitized cell according to claim 9 prepares dye-sensitized cell with combined counter electrode, special
Sign is：Light anode is to adsorb the titanium dioxide electrodes of N719 dyestuffs；The electrolyte is includes 0.2M 1- propyl -3- methyl
Iodate imidazoles, 0.05M iodine, 0.1M lithium iodides, 0.2M tetrabutylammonium iodides and 0.5M 4- tert .-butylpyridines acetonitrile solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109036854A (en) * | 2018-07-31 | 2018-12-18 | 南京楚卿电子科技有限公司 | Organic dye sensitized type solar battery and preparation method thereof |
| CN109448998A (en) * | 2018-10-23 | 2019-03-08 | 陕西国防工业职业技术学院 | A kind of dye-sensitized solar cells are to electrode and preparation method thereof |
| CN111342769A (en) * | 2018-12-18 | 2020-06-26 | 苏州阿特斯阳光电力科技有限公司 | Photovoltaic outgoing line, and preparation method and application thereof |
| CN112852005A (en) * | 2020-12-30 | 2021-05-28 | 宁波益德新材料有限公司 | Graphene/polyimide microcrystalline ball composite material and preparation method and application thereof |
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2017
- 2017-12-27 CN CN201711448716.8A patent/CN108172401A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109036854A (en) * | 2018-07-31 | 2018-12-18 | 南京楚卿电子科技有限公司 | Organic dye sensitized type solar battery and preparation method thereof |
| CN109448998A (en) * | 2018-10-23 | 2019-03-08 | 陕西国防工业职业技术学院 | A kind of dye-sensitized solar cells are to electrode and preparation method thereof |
| CN111342769A (en) * | 2018-12-18 | 2020-06-26 | 苏州阿特斯阳光电力科技有限公司 | Photovoltaic outgoing line, and preparation method and application thereof |
| CN112852005A (en) * | 2020-12-30 | 2021-05-28 | 宁波益德新材料有限公司 | Graphene/polyimide microcrystalline ball composite material and preparation method and application thereof |
| CN112852005B (en) * | 2020-12-30 | 2022-04-22 | 宁波益德新材料有限公司 | Graphene/polyimide microcrystalline ball composite material and preparation method and application thereof |
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