CN104425135B - Preparation method and applications of the redox graphene to electrode - Google Patents

Preparation method and applications of the redox graphene to electrode Download PDF

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CN104425135B
CN104425135B CN201310401152.8A CN201310401152A CN104425135B CN 104425135 B CN104425135 B CN 104425135B CN 201310401152 A CN201310401152 A CN 201310401152A CN 104425135 B CN104425135 B CN 104425135B
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oxide
preparation
nano titanium
graphene oxide
titanium oxide
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CN104425135A (en
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贺蒙
殷雄
吴凡
徐鹏
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2045Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2095Light-sensitive devices comprising a flexible sustrate
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/542Dye sensitized solar cells

Abstract

The invention provides a kind of preparation method and applications of redox graphene to electrode.The preparation method includes:Dispersion containing graphene oxide and nano titanium oxide in conductive substrates and is removed into the dispersant of the dispersion liquid containing graphene oxide and nano titanium oxide, so as in the conductive substrates Surface Creation primary membrane, then ultraviolet light is carried out to the primary membrane, so as to obtain redox graphene film.The method provided using the present invention prepares redox graphene to electrode it is possible to prevente effectively from reacting brought unsafe factor using toxic chemical or under high temperature, high pressure, environment-friendly and step is simple, can be used for preparing redox graphene to electrode on a large scale.

Description

Preparation method and applications of the redox graphene to electrode
Technical field
The present invention relates to a kind of preparation method and applications of redox graphene to electrode.
Background technology
With the sustainable development of social economy, energy crisis and increasingly sharpening for environmental pollution turn into global human institute The serious problems faced.Solar energy is inexhaustible, nexhaustible, from the energy for a long time with it is environment-friendly from the point of view of, using too Sun can be one of most safe, most environmentally friendly and most long-range method.Compared with silicon solar cell, DSSC (Dye-sensitized Solar Cells)Have the advantages that cheap, stability is good and it is simple to prepare, with good application Prospect.
DSSC is mainly constituted by the semiconductor optical anode of absorption dyestuff, electrolyte and to electrode.It is right Electrode is as the major part of DSSC, and redox in original electrolyte is gone back in main transmission electronics and catalysis Electricity is right(I3ˉ/Iˉ)Effect.Due to metal platinum(Pt)It is right to electrolyte redox electricity(I3ˉ/Iˉ)With high catalytic performance, Thus as conventional at present to electrode material.However, applied metal Pt is as to electrode material, having three below disadvantage End:First, Pt metal price are expensive;Second, pyrolytic, which prepares Pt, can not meet the preparation of flexible battery to the method for electrode It is required that;3rd, Pt metal are easily and I3- react and be corroded, decline its catalytic performance.Therefore, grind both at home and abroad in the last few years The persons of studying carefully put forth effort to find cheap, efficient platinum alternative materials as DSSC to electrode, so as to promote this kind of The extensive use of battery.
Graphene oxide is the oxide of graphene, generally by graphite powder through Strong oxdiative and peel off be made, be one kind by list Oxygen-containing functional group is contained on layer to surface and edge that tens layers are not waited(Such as hydroxyl, carboxyl, epoxy radicals)Graphene sheet layer composition Layer structure.Resulting redox graphene is conductive after carrying out reduction for graphene oxide, translucency and catalysis Performance, makes it have the potentiality to electrode material as DSSC.At present, that has reported is used as to electrode The redox graphene of material can be obtained by various means such as electronation, thermal annealing decomposition or hydro-thermals.Wherein, it is chemical Reducing process is that strong reductant is added into graphene oxide solution, and such as hydrazine hydrate, sodium borohydride are reduced to it.Heat is moved back Fiery decomposition method is that graphene oxide powder is placed in hot environment, and the oxygen-containing functional group on its surface is removed using pyroprocess. Hydro-thermal method is to add graphene oxide and other organic or inorganic go back original reagents in reactor, is reacted under high temperature, high pressure, So that the oxygen-containing functional group of graphene oxide is reduced.Redox graphene is prepared to electrode needs using chemical reduction method Using strong reductant, such as hydrazine hydrate, these go back original reagents have strong toxicity and corrosivity.And in addition in two methods, The reaction condition of HTHP is needed to use, preparation condition is more harsh and complicated.Therefore, also need that development condition is gentle, environment Friendly simple and easy method prepares redox graphene to electrode.
The content of the invention
The invention aims to overcome to prepare redox graphene to electrode process needs using existing method Using toxic chemical or the deficiency of severe reaction conditions, and provide a kind of preparation condition gentle, environment-friendly reduction Simple method for preparing and its application of the graphene oxide to electrode.
The invention provides a kind of preparation method of redox graphene to electrode, wherein, this method includes:It will contain The dispersion of graphene oxide and nano titanium oxide containing graphene oxide and is received in conductive substrates, and described in removal Dispersant in the dispersion liquid of rice titanium dioxide, so that primary membrane is formed on the conductive substrates surface, and to the primary membrane Ultraviolet light is carried out, so as to obtain redox graphene film.
The redox graphene prepared present invention also offers the method for the invention is to electrode in dye sensitization Application in solar cell.
It was found by the inventors of the present invention that it is usual to electrode that redox graphene is prepared using method of the prior art Toxic chemical is needed to use, or needs to carry out under the harsh conditions such as high temperature, high pressure, and these preparation methods are not easy to Large-scale production.And the redox graphene that the present invention is provided dexterously has evaded these complicated mistakes to the preparation method of electrode Journey, irradiates under ultraviolet light using by the compound of graphene oxide and titanium dioxide, the electronics inspired using titanium dioxide Graphene oxide is reduced and redox graphene is obtained.The preparation method that the present invention is provided is easy, mild condition, It is environment-friendly, with good prospects for commercial application.In addition, the redox graphene prepared using the method for the present invention Advantage to electrode is also resided in, because preparation method does not need high-temperature process, therefore, it can the reduction-oxidation of the present invention Grapheme material is prepared in flexible macromolecule conductive substrates, flexibility is made to electrode, using more extensive.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is DSSC T1 prepared by test case 1,2 and 3(Using to electrode CE1), dye sensitization is too Positive energy battery T2(Using to electrode CE2)With DSSC T3(Using to electrode CE3)In 100mW/cm2Mould Intend photoelectric current-voltage curve under sunshine irradiation.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The redox graphene that the present invention is provided includes to the preparation method of electrode:Graphene oxide and nanometer will be contained The dispersion of titanium dioxide is removed described scattered containing graphene oxide and nano titanium oxide in conductive substrates Dispersant in liquid, so as to form primary membrane on the conductive substrates surface, and carries out ultraviolet light to the primary membrane, from And obtain redox graphene film.
In the present invention, the preparation method of the dispersion liquid containing graphene oxide and nano titanium oxide is not special Limit, as long as ensure that graphene effectively, fully disperses in dispersant.According to a kind of preferred reality of the present invention Mode is applied, the preparation method includes:Graphene oxide dispersion can be mixed with nano titanium oxide dispersion.It is further preferred that It is described containing graphene oxide and receiving for the ease of the preparation of the dispersion liquid containing graphene oxide and nano titanium oxide The preparation method of the dispersion liquid of rice titanium dioxide includes:Graphene oxide dispersion is mixed with nano titanium oxide, it is further preferred that Nano titanium oxide is added into graphene oxide dispersion, and is well mixed.In order that its dispersion effect is more preferably, it is preferably above-mentioned Progress under the conditions of stirring or ultrasonic disperse is blended in, as long as the time of mixing ensures graphene oxide and nano titanium oxide point Dissipate uniform.
In the present invention, the graphene oxide is dense in the dispersion liquid containing graphene oxide and nano titanium oxide The selectable range of degree is wider, according to one kind of the invention preferred embodiment, and the graphene oxide is containing oxidation stone Concentration in the dispersion liquid of black alkene and nano titanium oxide is 0.1mg/mL-1mg/mL, more preferably 0.2mg/mL-0.9mg/ mL。
In the present invention, the structure of the graphene oxide can be single layer structure or sandwich construction(The number of plies can be 2-100 layers).
Wherein, the graphene oxide dispersion can be with commercially available, it would however also be possible to employ well known to a person skilled in the art Method is prepared.
According to the present invention, the kind of the dispersant formed in the dispersion liquid containing graphene oxide and nano titanium oxide Class can be conventional use of dispersant in this area.For example, the dispersant can be water, ethanol, isopropanol, dimethyl methyl One or more in acid amides and acetone.When the dispersant is mixed dispersant, it can be mixed between different dispersant components It is molten, for example, the mixed dispersant can be water-ethanol.In order to subsequently be easy to remove dispersant, and dispersant used Toxicity is relatively low, it is preferable that the dispersant is ethanol.
According to the present invention, for preparing the graphene point used in the dispersion liquid containing graphene oxide and nano titanium oxide The selection of the species of dispersant is that those skilled in the art are conventional use of in dispersion liquid or above-mentioned nano titanium oxide dispersion Dispersant, as set forth above, it is possible to the one or more in water, ethanol, isopropanol, dimethylformamide and acetone, preferably For ethanol.
In addition, nano titanium oxide dispersion can also be commercially available or using well known to a person skilled in the art method Preparation method.
In the embodiment that the present invention is selected, the nano titanium oxide is the titanium dioxide granule that particle diameter is 1-100nm, Or be the titanium dioxide platelets of { 001 } crystal face that thickness is 1-100nm.
According to the present invention, the nano titanium oxide is in the dispersion liquid containing graphene oxide and nano titanium oxide In concentration selectable range it is wider, under preferable case, the nano titanium oxide is described containing graphene oxide and receiving Concentration in the dispersion liquid of rice titanium dioxide is graphene oxide in the dispersion liquid containing graphene oxide and nano titanium oxide 1-7 times of middle concentration, preferably 2-5 times.
The present invention to by the dispersion containing graphene oxide and nano titanium oxide in conductive substrates There is no particular limitation for method, for example, can be the methods such as conventional spin coating, spraying or showering.In order that obtain to electrode Material film is more uniformly distributed, preferably spin coating.
According to the present invention, the side of the dispersant in the dispersion liquid containing graphene oxide and nano titanium oxide is removed The method that method can be known to the skilled person, for example, can be in room temperature(20-40℃)It is lower to volatilize or dry naturally Etc. method.Do not refer to utterly remove it should be noted that dispersant is removed, but remove usual to those skilled in the art The amount of acceptable dispersant in the primary membrane of the formation of understanding, for example, on the basis of the gross mass of the primary membrane, dispersant Content be not higher than 5 weight %.In addition, the assay method of dispersant may be referred to people in the art in the primary membrane The known method of member is carried out, and will not be repeated here.
According to the present invention, the primary membrane refer to the compound of graphene oxide and nano titanium oxide it is coated after The film formed in conductive substrates.The amount of the dispersion liquid and the method for coating of coating make the film of obtained primary membrane thick Degree is general in the range of 20 nanometers to one microns.The thickness of the primary membrane can pass through SEM Observed.
The present invention is to by the condition of primary membrane progress ultraviolet light, there is no particular limitation, as long as enabling to oxygen Graphite alkene is reduced to redox graphene.The condition of described ultraviolet light generally include ultraviolet light wavelength and Light application time, the wavelength of the ultraviolet light can be 4-380nm, and light application time can be 1-12 hours.Effect is prepared in order to improve Rate, it is preferable that the wavelength of ultraviolet light is 350-380nm, light application time is 2-4 hours.For producing the equipment of ultraviolet light without spy Other to limit, all wavelength that produce can be as light source in 4-380nm ultra-violet apparatus.In addition, in the present invention, by institute State primary membrane and carry out the process of ultraviolet light in room temperature(Such as, 20-40 DEG C)Lower progress can be realized to enter graphene oxide Row reduces and obtains redox graphene.It therefore, it can realize well and reduction prepared in flexible macromolecule conductive substrates Graphene oxide composite material.Graphene oxide have been converted into redox graphene this conversion can by Raman spectrum, The conventional technical means such as XPS are confirmed, will not be repeated here.
According to the present invention, the material category and thickness of the conductive substrates can be the conventional selection of this area, for example, The thickness of the conductive substrates can be 0.2-3mm.The conductive substrates material can be the tin ash selected from fluorine doped(Letter Claim:FTO)Electro-conductive glass, tin indium oxide(Referred to as:ITO)Electro-conductive glass, the polyethylene terephthalate for plating tin indium oxide (Referred to as:PET-ITO)With the PEN of plating tin indium oxide(Referred to as:PEN-ITO)In one or more.
The redox graphene prepared present invention also offers the method for the invention is to electrode in dye sensitization Application in solar cell.Redox graphene of the present invention is being used for DSSC to electrode Preparation when, except using redox graphene of the present invention to electrode in addition to, the DSSC Preparation method and miscellaneous part it is known to those skilled in the art, will not be repeated here.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme Monotropic type, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.
The present invention will be further described in detail by specific embodiment below.
Instrument title and model used in following test cases:What Oriel Newport companies produced is furnished with 300W xenon lamps Solar simulator and Keithley companies production 2420 type digital sourcemeters.
Embodiment 1
The embodiment is used to illustrate preparation method of the redox graphene of the invention provided to electrode.
(1)The preparation of dispersion liquid containing graphene oxide and nano titanium oxide
Take graphene oxide dispersions of the 20ml using ethanol as dispersant(Graphene oxide concentration is 0.3mg/ml, purchase From Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that will be equipped with the graphene oxide dispersion is stirred as magnetic force Mix and stirred on device, 30mg model P25 is added thereto(Particle diameter is 21nm, purchased from German Evonik Degussa Corp.)'s Titanium dioxide nanoparticle, then stirs 24 hours, obtains the dispersion liquid containing graphene oxide and nano titanium oxide.
(2)Preparation of the redox graphene to electrode
5ml is taken to pass through step(1)The obtained dispersion liquid containing graphene oxide and nano titanium oxide, passes through spin coating Mode(Each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s)It is coated in 12cm2 FTO electro-conductive glass(Purchase in Japanese Nippon Sheet Glass companies, thickness is 2.2mm, surface resistance is 15 Ω/sq) On, after ethanol volatilizees naturally, graphene oxide-nano titanium oxide forms uniform thickness on FTO electro-conductive glass and is 200nm faint yellow primary membrane.Then in room temperature(25℃)Under, above-mentioned primary membrane is placed on ultraviolet lamp(Wavelength is 365nm) Lower irradiation 2 hours, during this, flaxen primary membrane becomes black, shows that graphene oxide receives titanium dioxide through purple Outer light excites the electronics of generation and is reduced, as redox graphene.Thus prepare including FTO electro-conductive glass and attached Redox graphene on the FTO electro-conductive glass to electrode CE1.
Embodiment 2
The embodiment is used to illustrate preparation method of the redox graphene of the invention provided to electrode.
(1)The preparation of dispersion liquid containing graphene oxide and nano titanium oxide
Take graphene oxide dispersions of the 20ml using ethanol as dispersant(Graphene oxide concentration is 0.9mg/ml, purchase From Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that will be equipped with the graphene oxide dispersion is stirred as magnetic force Mix and stirred on device, 36mg model P90 is added thereto(Particle diameter is 14nm, purchased from German Evonik Degussa Corp.)'s Titanium dioxide nanoparticle, then stirs 24 hours, obtains the dispersion liquid containing graphene oxide and nano titanium oxide.
(2)Preparation of the redox graphene to electrode
5ml is taken to pass through step(1)The obtained dispersion liquid containing graphene oxide and nano titanium oxide, passes through spin coating Mode(Each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s)It is coated in 12cm2 FTO electro-conductive glass(Thickness is 0.5mm, and surface resistance is 20 Ω/sq)On, after ethanol volatilizees naturally, graphene oxide-nanometer Titanium dioxide forms the faint yellow primary membrane that uniform thickness is 150nm on FTO electro-conductive glass.Then in room temperature(25℃) Under, above-mentioned primary membrane is placed on ultraviolet lamp(Wavelength is 365nm)Lower irradiation 4 hours, during this, flaxen primary membrane Become black, show that graphene oxide receives titanium dioxide and is reduced through the electronics that ultraviolet excitation is produced, as oxygen reduction Graphite alkene.Thus prepare including FTO electro-conductive glass and the redox graphene being attached on the FTO electro-conductive glass To electrode CE2.
Embodiment 3
The embodiment is used to illustrate preparation method of the redox graphene of the invention provided to electrode.
(1)The preparation of dispersion liquid containing graphene oxide and nano titanium oxide
Take graphene oxide dispersions of the 20ml using ethanol as dispersant(Graphene oxide concentration is 0.9mg/ml, purchase From Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that will be equipped with the graphene oxide dispersion is stirred as magnetic force Mix and stirred on device, 36mg model P90 is added thereto(Particle diameter is 14nm, purchased from German Evonik Degussa Corp.)'s Titanium dioxide nanoparticle, then stirs 24 hours, obtains the dispersion liquid containing graphene oxide and nano titanium oxide.
(2)Preparation of the redox graphene to electrode
5ml is taken to pass through step(1)The obtained dispersion liquid containing graphene oxide and nano titanium oxide, passes through spin coating Mode(Each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s)It is coated in 12cm2 PEN-ITO flexible conductive substrates(Thickness is 0.125mm, and surface resistance is 50 Ω/sq, purchased from Hong Kong Kintec companies)On, treat After ethanol volatilizees naturally, it is 180nm's that graphene oxide-nano titanium oxide forms uniform thickness on FTO electro-conductive glass Faint yellow primary membrane.Then in room temperature(25℃)Under, above-mentioned primary membrane is placed on ultraviolet lamp(Wavelength is 365nm)Lower irradiation 4 Hour, during this, flaxen primary membrane becomes black, shows that graphene oxide receives titanium dioxide through ultraviolet excitation The electronics of generation and be reduced, as redox graphene.Thus prepare including PEN conductive substrates and be attached to described Redox graphene in PEN conductive substrates to electrode CE3.
Test case 1
The test case is used for the preparation and its performance test for illustrating DSSC.
Dyestuff N3 will be adsorbed with(Purchased from Solaronix companies of Switzerland)TiO2Porous film electrode(TiO2Colloid is purchased from auspicious Scholar Solaronix Wuhan Ge Ao companies)It is placed on clean table top, and it is 0.6cm × 0.6cm apertures that will accomplish fluently size Surlyn1702(Purchased from Solaronix companies of Switzerland, thickness is 25 μm)Heat-sealing film overlays above-mentioned TiO2Porous film electrode On, electrolyte is added dropwise into aperture(The constituent of electrolyte is 0.05mol/L iodine, 0.5mol/L lithium iodides, 0.3mol/L The N- tolimidazoles of 1- hexyl -3- methylimidazoles iodine, 0.5mol/L tert .-butylpyridines and 0.3mol/L, solvent is 3- methoxies Base propionitrile), then to electrode CE1 in heat-sealing film surface cover, and in the TiO for being adsorbed with dyestuff N32Porous film electrode appearance Put on face with the steel die that aperture is 0.4cm × 0.5cm as mask(mask), thus obtain dye sensitization of solar Battery T1.
DSSC T1 is in 100mW/cm2Simulated solar light irradiation under photoelectric current-voltage curve such as Shown in Fig. 1.
From figure 1 it appears that DSSC T1 open-circuit photovoltage is 0.665V, short-circuit photocurrent For 16.18mA/cm2, fill factor, curve factor is 0.37, and photoelectric transformation efficiency is 3.98%.
Test case 2
The test case is used for the preparation and its performance test for illustrating DSSC.
Method according to test case 1 prepares DSSC and its performance is tested, unlike, institute State and electrode CE1 is substituted with to electrode CE2, obtain DSSC T2.
DSSC T2 is in 100mW/cm2Simulated solar light irradiation under photoelectric current-voltage curve such as Shown in Fig. 1.
From figure 1 it appears that DSSC T2 open-circuit photovoltage is 0.665V, short-circuit photocurrent For 15.94mA/cm2, fill factor, curve factor is 0.41, and photoelectric transformation efficiency is 4.35%.
Test case 3
The test case is used for the preparation and its performance test for illustrating DSSC.
Method according to test case 1 prepares DSSC and its performance is tested, unlike, institute State and electrode CE1 is substituted with to electrode CE3, obtain DSSC T3.
DSSC T3 open-circuit photovoltage is 0.610V, and short-circuit photocurrent is 13.28mA/cm2, fill out It is 0.34 to fill the factor, and photoelectric transformation efficiency is 2.75%.
As can be seen from the above embodiments, electrode need not be made to prepare redox graphene using the method for the present invention With toxic chemical, without harsh conditions such as high temperature, high pressures, but use the compound of graphene oxide and titanium dioxide Thing is irradiated under ultraviolet light, and the electronics inspired using titanium dioxide is reduced to graphene oxide and obtains oxygen reduction fossil Black alkene.Preparation method that the present invention is provided is easy, mild condition and environment-friendly.Furthermore, it is possible to by the present invention the reduction Graphene oxide composite material is prepared in flexible macromolecule conductive substrates, flexibility is made to electrode, using more extensive.
The redox graphene prepared using the method for the present invention can be seen that by the result of above-mentioned test case Material may be used as DSSC to electrode material.I.e., it is possible to which effectively catalytic oxidation-reduction electricity is right, make dyestuff Sensitization solar battery normal power generation under illumination condition, and with certain electricity conversion.Thus illustrate, using this hair Redox graphene prepared by bright method has good photoelectric properties to the DSSC of electrode assembling, And with wide prospects for commercial application.

Claims (12)

1. a kind of redox graphene is to the preparation method of electrode, it is characterised in that this method includes:Graphite oxide will be contained The dispersion of alkene and nano titanium oxide contains graphene oxide and nanometer titanium dioxide in conductive substrates, and described in removal Dispersant in the dispersion liquid of titanium, so as to form primary membrane on the conductive substrates surface, and is carried out ultraviolet to the primary membrane Light irradiation, so as to obtain redox graphene film.
2. preparation method according to claim 1, wherein, it is described scattered containing graphene oxide and nano titanium oxide The preparation method of liquid includes:Graphene oxide dispersion is mixed with nano titanium oxide, or by graphene oxide dispersion Mixed with nano titanium oxide dispersion, obtain the dispersion liquid containing graphene oxide and nano titanium oxide.
3. preparation method according to claim 1 or 2, wherein, the graphene oxide containing graphene oxide and is being received Concentration in the dispersion liquid of rice titanium dioxide is 0.1mg/mL-1mg/mL.
4. preparation method according to claim 1 or 2, wherein, the dispersant in dispersion liquid is water, ethanol, isopropanol, two One or more in NMF and acetone.
5. preparation method according to claim 4, wherein, the dispersant in dispersion liquid is ethanol.
6. preparation method according to claim 1 or 2, wherein, the nano titanium oxide is two that particle diameter is 1-100nm Titan oxide particles or be { 001 } crystal face that thickness is 1-100nm titanium dioxide platelets.
7. preparation method according to claim 1 or 2, wherein, the nano titanium oxide contains graphite oxide described Concentration in the dispersion liquid of alkene and nano titanium oxide is graphene oxide containing graphene oxide and nano titanium oxide 1-7 times of concentration in dispersion liquid.
8. preparation method according to claim 7, wherein, the nano titanium oxide it is described containing graphene oxide and Concentration in the dispersion liquid of nano titanium oxide is graphene oxide scattered containing graphene oxide and nano titanium oxide 2-5 times of concentration in liquid.
9. preparation method according to claim 1, wherein, the condition of ultraviolet light includes:The wavelength of ultraviolet light is 4- 380nm, light application time is 1-12 hours.
10. preparation method according to claim 9, wherein, the condition of ultraviolet light includes:The wavelength of ultraviolet light is 350-380nm, light application time is 2-5 hours.
11. preparation method according to claim 1, wherein, the thickness of the conductive substrates is 0.2-3mm;The conduction Substrate is the tin dioxide conductive glass selected from fluorine doped, indium tin oxide-coated glass, the poly terephthalic acid second for plating tin indium oxide One or more in the PEN of diol ester and plating tin indium oxide.
12. the redox graphene that any one methods described is prepared in claim 1-11 is to electrode in dye sensitization Application in solar cell.
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