CN104425135A - Preparation method for reduced graphene oxide counter electrode and application thereof - Google Patents
Preparation method for reduced graphene oxide counter electrode and application thereof Download PDFInfo
- Publication number
- CN104425135A CN104425135A CN201310401152.8A CN201310401152A CN104425135A CN 104425135 A CN104425135 A CN 104425135A CN 201310401152 A CN201310401152 A CN 201310401152A CN 104425135 A CN104425135 A CN 104425135A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- preparation
- oxide
- nano titanium
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01G9/2045—Light-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
-
- 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
- H01G9/2095—Light-sensitive devices comprising a flexible sustrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention provides a preparation method for a reduced graphene oxide counter electrode and application thereof. The preparation method includes the following steps: dispersion containing graphene oxide and nano-titanium dioxide is coated on a conducting substrate and the dispersing agent of the dispersion containing the graphene oxide and the nano-titanium dioxide is removed, so that a primary membrane is formed on the surface of the conducting substrate, and the primary membrane is then irradiated by ultraviolet light, so that a reduced graphene oxide film is obtained. The adoption of the method provided by the invention to prepare the reduced graphene oxide counter electrode can effectively avoid unsafe factors caused by the usage of toxic chemical reagents or reaction under high temperature and high pressure, the preparation method is environment-friendly, moreover, the steps are simple, and the preparation method can be used for preparing the reduced graphene oxide counter electrode on a large scale.
Description
Technical field
The present invention relates to a kind of redox graphene to the preparation method of electrode and application thereof.
Background technology
Along with socioeconomic sustainable development, the increasingly sharpening of energy crisis and environmental pollution becomes the serious problems that global human faces.Solar energy is inexhaustible, nexhaustible, considers from the energy is permanent with eco-friendly angle, utilizes solar energy to be the safest, most environmental protection and one of the most long-range method.Compared with silicon solar cell, DSSC (Dye-sensitized Solar Cells) has the advantages such as cheapness, good stability and preparation be simple, has good application prospect.
DSSC primarily of absorbing dye semiconductor optical anode, electrolyte and electrode is formed.To the major part of electrode as DSSC, mainly play oxidation-reduction pair (I in transmission electronic and catalytic reduction electrolyte
3-/I-) effect.Because metal platinum (Pt) is electric to (I to electrolyte redox
3-/I-) there is high catalytic performance, thus become at present conventional to electrode material.But applied metal Pt, as to electrode material, also exists following three drawbacks: the first, Pt metal price is expensive; The second, pyrolysis prepares Pt cannot meet flexible battery preparation requirement to the method for electrode; Three, Pt metal easily and I
3-react and be corroded, its catalytic performance is declined.Therefore, researchers puted forth effort to find cheap, efficient platinum substitution material as DSSC to electrode both at home and abroad in the last few years, thus advanced the extensive use of this kind of battery.
Graphene oxide is the oxide of Graphene, usually being obtained through Strong oxdiative and stripping by graphite powder, is a kind of layer structure be made up of to the graphene sheet layer that oxygen-containing functional group (as hydroxyl, carboxyl, epoxy radicals) is contained on the surface that tens layers does not wait and edge individual layer.The redox graphene that graphene oxide obtains after reduction has conductivity, light transmission and catalytic performance, makes it have as the potentiality of DSSC to electrode material.At present, can be used as of having reported can be obtained by various means such as electronation, thermal annealing decomposition or hydro-thermals the redox graphene of electrode material.Wherein, chemical reduction method adds strong reductant in graphene oxide solution, as hydrazine hydrate, sodium borohydride etc. reduce to it.Thermal annealing decomposition method is that graphene oxide powder is placed in hot environment, utilizes pyroprocess to remove the oxygen-containing functional group on its surface.Hydro thermal method be by graphene oxide and other organic or inorganic also original reagent add in reactor, react under high temperature, high pressure, the oxygen-containing functional group of graphene oxide be reduced.Adopt chemical reduction method to prepare redox graphene to need to use strong reductant, such as hydrazine hydrate to electrode, these are gone back original reagent and have strong toxicity and corrosivity.And in other two kinds of methods, all needing the reaction condition using HTHP, preparation condition is comparatively harsh and complicated.Therefore, also need that development condition is gentle, eco-friendly simple and easy method prepares redox graphene to electrode.
Summary of the invention
The object of the invention is to overcome the deficiency adopting existing method to prepare redox graphene to need to use toxic chemical or severe reaction conditions to electrode process, and provide that a kind of preparation condition is gentle, eco-friendly redox graphene is to the simple method for preparing of electrode and application thereof.
The invention provides the preparation method of a kind of redox graphene to electrode, wherein, the method comprises: by the dispersion containing graphene oxide and nano titanium oxide in conductive substrates, and the dispersant removed in the described dispersion liquid containing graphene oxide and nano titanium oxide, thus form primary membrane on described conductive substrates surface, and UV-irradiation is carried out to described primary membrane, thus obtain redox graphene film.
Present invention also offers redox graphene that the method for the invention prepares to the application of electrode in DSSC.
The present inventor finds, adopt method of the prior art usually to need to use toxic chemical to electrode to prepare redox graphene, or need to carry out under the harsh conditions such as high temperature, high pressure, and these preparation methods is not easy to large-scale production.And redox graphene provided by the invention has evaded these complex processes dexterously to the preparation method of electrode, adopt and irradiated under ultraviolet light by the compound of graphene oxide and titanium dioxide, the duplet graphene oxide utilizing titanium dioxide to inspire carries out reducing and obtaining redox graphene.This preparation method provided by the invention is easy, mild condition, and environmental friendliness has good prospects for commercial application.In addition, the advantage of redox graphene to electrode adopting method of the present invention to prepare also is, because preparation method does not need high-temperature process, therefore, can described redox graphene material of the present invention be prepared in flexible macromolecule conductive substrates, make flexible to electrode, apply more extensive.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 be test case 1,2 and 3 prepare DSSC T1(adopt to electrode CE1), DSSC T2(adopt to electrode CE2) and DSSC T3(employing to electrode CE3) at 100mW/cm
2simulated solar irradiation irradiate under photoelectric current-voltage curve.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Redox graphene provided by the invention is the preparation method to electrode comprise: by the dispersion containing graphene oxide and nano titanium oxide in conductive substrates, and the dispersant removed in the described dispersion liquid containing graphene oxide and nano titanium oxide, thus form primary membrane on described conductive substrates surface, and UV-irradiation is carried out to described primary membrane, thus obtain redox graphene film.
In the present invention, the described preparation method containing the dispersion liquid of graphene oxide and nano titanium oxide is not particularly limited, as long as can ensure that Graphene effectively, fully disperses in dispersant.According to one of the present invention preferred embodiment, this preparation method comprises: graphene oxide dispersion can be mixed with nano titanium oxide dispersion.More preferably, for the ease of the described preparation containing the dispersion liquid of graphene oxide and nano titanium oxide, the described preparation method containing the dispersion liquid of graphene oxide and nano titanium oxide comprises: graphene oxide dispersion mixed with nano titanium oxide, more preferably, in graphene oxide dispersion, add nano titanium oxide, and mix.In order to make its dispersion effect better, preferably above-mentioned being blended in is stirred or is carried out under ultrasonic disperse condition, as long as the time of mixing ensures that graphene oxide and nano titanium oxide are uniformly dispersed.
In the present invention, the selectable range of the concentration of described graphene oxide in the dispersion liquid containing graphene oxide and nano titanium oxide is wider, according to one of the present invention preferred embodiment, the concentration of described graphene oxide in the dispersion liquid containing graphene oxide and nano titanium oxide is 0.1mg/mL-1mg/mL, is more preferably 0.2mg/mL-0.9mg/mL.
In the present invention, the structure of described graphene oxide can be single layer structure or sandwich construction (number of plies can be 2-100 layer).
Wherein, described graphene oxide dispersion can be commercially available, and the method for well known to a person skilled in the art also can be adopted to prepare.
According to the present invention, the kind forming the dispersant in the described dispersion liquid containing graphene oxide and nano titanium oxide can be the conventional dispersant used in this area.Such as, described dispersant can be one or more in water, ethanol, isopropyl alcohol, dimethyl formamide and acetone.When described dispersant is mixed dispersant, can be miscible between different dispersant component, such as, described mixed dispersant can be water-ethanol.In order to dispersant is removed by follow-up being easy to, and the toxicity of dispersant used is lower, and preferably, described dispersant is ethanol.
According to the present invention, in the graphene dispersing solution used for the preparation of the dispersion liquid containing graphene oxide and nano titanium oxide or above-mentioned nano titanium oxide dispersion dispersant kind be chosen as the dispersant that those skilled in the art's routine uses, as mentioned above, can be selected from water, ethanol, isopropyl alcohol, dimethyl formamide and acetone one or more, be preferably ethanol.
In addition, nano titanium oxide dispersion can also commercially available or adopt well known to a person skilled in the art method preparation method.
In the execution mode of the present invention's choosing, the titanium dioxide granule of described nano titanium oxide to be particle diameter be 1-100nm, or for thickness be the { titanium dioxide platelets of 001} crystal face of 1-100nm.
According to the present invention, the selectable range of the concentration of described nano titanium oxide in the described dispersion liquid containing graphene oxide and nano titanium oxide is wider, under preferable case, the concentration of described nano titanium oxide in the described dispersion liquid containing graphene oxide and nano titanium oxide is 1-7 times of graphene oxide concentration in the dispersion liquid containing graphene oxide and nano titanium oxide, is preferably 2-5 doubly.
The present invention, to by the method for the described dispersion containing graphene oxide and nano titanium oxide in conductive substrates, there is no particular limitation, such as, can be the methods such as the spin coating of routine, spraying or showering.More even to electrode material membrane in order to what make to obtain, be preferably spin coating.
According to the present invention, remove the method that the described method containing the dispersant in the dispersion liquid of graphene oxide and nano titanium oxide can be known to the skilled person, such as, naturally can volatilize under room temperature (20-40 DEG C) or the method such as oven dry.It should be noted that, dispersant is removed and does not refer to and remove utterly, but remove the amount of acceptable dispersant in the primary membrane of the formation usually understood to those skilled in the art, such as, with the gross mass of described primary membrane for benchmark, the content of dispersant is not higher than 5 % by weight.In addition, in described primary membrane, the assay method of dispersant can carry out with reference to the method for well known to a person skilled in the art, does not repeat them here.
According to the present invention, the film that the compound that described primary membrane refers to graphene oxide and nano titanium oxide is formed after coating in conductive substrates.The amount of described dispersion liquid and the method for coating of coating make the film thickness of the primary membrane obtained generally in the scope of 20 nanometers to a micron.The thickness of described primary membrane can be observed by scanning electron microscopy.
To the condition of described primary membrane being carried out UV-irradiation, there is no particular limitation, as long as graphene oxide can be made to be reduced to redox graphene in the present invention.The condition of described UV-irradiation generally includes wavelength and the light application time of ultraviolet light, and the wavelength of described ultraviolet light can be 4-380nm, and light application time can be 1-12 hour.In order to improve preparation efficiency, preferably, the wavelength of ultraviolet light is 350-380nm, and light application time is 2-4 hour.For the equipment producing ultraviolet light, there is no particular limitation, and all wavelength that produces all can be used as light source at the ultra-violet apparatus of 4-380nm.In addition, in the present invention, the process of described primary membrane being carried out UV-irradiation carries out namely can realizing reducing to graphene oxide and obtaining redox graphene under room temperature (e.g., 20-40 DEG C).Therefore, can realize well preparing redox graphene material in flexible macromolecule conductive substrates.This conversion that graphene oxide has been converted into redox graphene can be confirmed by the routine techniques such as Raman spectrum, XPS means, does not repeat them here.
According to the present invention, the material category of described conductive substrates and thickness can be all that the routine of this area is selected, and such as, the thickness of described conductive substrates can be 0.2-3mm.PET-ITO) and the PEN (abbreviation: one or more PEN-ITO) of plating tin indium oxide described conductive substrates material (can be called for short: FTO) electro-conductive glass, tin indium oxide (are called for short: ITO) PETG of electro-conductive glass, plating tin indium oxide (is called for short: for being selected from the tin ash mixing fluorine.
Present invention also offers redox graphene that the method for the invention prepares to the application of electrode in DSSC.When redox graphene of the present invention to be used for the preparation of DSSC to electrode, except adopting redox graphene of the present invention to except electrode, the preparation method of described DSSC and miscellaneous part are conventionally known to one of skill in the art, do not repeat them here.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned execution mode; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will be further described in detail the present invention by specific embodiment.
Instrument title used in following test case and model: the solar simulator being furnished with 300W xenon lamp that Oriel Newport company produces and the 2420 type digital sourcemeters that Keithley company produces.
Embodiment 1
This embodiment is for illustration of the preparation method of redox graphene provided by the invention to electrode.
(1) preparation of the dispersion liquid containing graphene oxide and nano titanium oxide
Get the graphene oxide dispersion of 20ml using ethanol as dispersant (graphene oxide concentration is 0.3mg/ml, purchased from Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that described graphene oxide dispersion is housed is stirred as on magnetic stirring apparatus, the model adding 30mg is wherein P25(particle diameter is 21nm, purchased from German Evonik Degussa Corp.) titanium dioxide nanoparticle, then stir 24 hours, obtain the dispersion liquid containing graphene oxide and nano titanium oxide.
(2) redox graphene is to the preparation of electrode
Get the dispersion liquid containing graphene oxide and nano titanium oxide that 5ml is obtained by step (1), be coated in 12cm by the mode (each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s) of spin coating
2fTO electro-conductive glass (purchase in Japanese Nippon Sheet Glass company, thickness is 2.2mm, surface resistance is 15 Ω/sq) on, after ethanol volatilizees naturally, graphene oxide-nano titanium oxide forms the faint yellow primary membrane that uniform thickness is 200nm on FTO electro-conductive glass.Then under room temperature (25 DEG C), irradiate 2 hours under above-mentioned primary membrane being placed on ultraviolet lamp (wavelength is 365nm), in this process, flaxen primary membrane becomes black, show that graphene oxide accepts electronics that titanium dioxide produces through ultraviolet excitation and is reduced, become redox graphene.Prepare thus comprise FTO electro-conductive glass and be attached to redox graphene on described FTO electro-conductive glass to electrode CE1.
Embodiment 2
This embodiment is for illustration of the preparation method of redox graphene provided by the invention to electrode.
(1) preparation of the dispersion liquid containing graphene oxide and nano titanium oxide
Get the graphene oxide dispersion of 20ml using ethanol as dispersant (graphene oxide concentration is 0.9mg/ml, purchased from Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that described graphene oxide dispersion is housed is stirred as on magnetic stirring apparatus, the model adding 36mg is wherein P90(particle diameter is 14nm, purchased from German Evonik Degussa Corp.) titanium dioxide nanoparticle, then stir 24 hours, obtain the dispersion liquid containing graphene oxide and nano titanium oxide.
(2) redox graphene is to the preparation of electrode
Get the dispersion liquid containing graphene oxide and nano titanium oxide that 5ml is obtained by step (1), be coated in 12cm by the mode (each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s) of spin coating
2fTO electro-conductive glass (thickness is 0.5mm, and surface resistance is 20 Ω/sq) on, after ethanol volatilizees naturally, graphene oxide-nano titanium oxide forms the faint yellow primary membrane that uniform thickness is 150nm on FTO electro-conductive glass.Then under room temperature (25 DEG C), irradiate 4 hours under above-mentioned primary membrane being placed on ultraviolet lamp (wavelength is 365nm), in this process, flaxen primary membrane becomes black, show that graphene oxide accepts electronics that titanium dioxide produces through ultraviolet excitation and is reduced, become redox graphene.Prepare thus comprise FTO electro-conductive glass and be attached to redox graphene on described FTO electro-conductive glass to electrode CE2.
Embodiment 3
This embodiment is for illustration of the preparation method of redox graphene provided by the invention to electrode.
(1) preparation of the dispersion liquid containing graphene oxide and nano titanium oxide
Get the graphene oxide dispersion of 20ml using ethanol as dispersant (graphene oxide concentration is 0.9mg/ml, purchased from Nanjing pioneer Nono-material Science & Technology Ltd.).The sample bottle that described graphene oxide dispersion is housed is stirred as on magnetic stirring apparatus, the model adding 36mg is wherein P90(particle diameter is 14nm, purchased from German Evonik Degussa Corp.) titanium dioxide nanoparticle, then stir 24 hours, obtain the dispersion liquid containing graphene oxide and nano titanium oxide.
(2) redox graphene is to the preparation of electrode
Get the dispersion liquid containing graphene oxide and nano titanium oxide that 5ml is obtained by step (1), be coated in 12cm by the mode (each spin coating amount is 100 μ l, and spin speed is 1000r/min, and each spin-coating time is 35s) of spin coating
2pEN-ITO flexible conductive substrates (thickness is 0.125mm, surface resistance is 50 Ω/sq, purchased from Hong Kong Kintec company) on, after ethanol volatilizees naturally, graphene oxide-nano titanium oxide forms the faint yellow primary membrane that uniform thickness is 180nm on FTO electro-conductive glass.Then under room temperature (25 DEG C), irradiate 4 hours under above-mentioned primary membrane being placed on ultraviolet lamp (wavelength is 365nm), in this process, flaxen primary membrane becomes black, show that graphene oxide accepts electronics that titanium dioxide produces through ultraviolet excitation and is reduced, become redox graphene.Prepare thus comprise PEN conductive substrates and be attached to redox graphene in described PEN conductive substrates to electrode CE3.
Test case 1
This test case is for illustration of the preparation of DSSC and performance test thereof.
Dyestuff N3(will be adsorbed with purchased from Solaronix company of Switzerland) TiO
2porous film electrode (TiO
2colloid is purchased from Switzerland Solaronix Wuhan Ge Ao company) be placed on clean table top, and will accomplish fluently be of a size of 0.6cm × 0.6cm aperture Surlyn1702(purchased from Solaronix company of Switzerland, thickness is 25 μm) heat-sealing film overlays above-mentioned TiO
2on porous film electrode, in aperture, dripping electrolyte, (constituent of electrolyte is the N-tolimidazole of 0.05mol/L iodine, 0.5mol/L lithium iodide, the 1-hexyl-3-methylimidazole iodine of 0.3mol/L, 0.5mol/L tert .-butylpyridine and 0.3mol/L, solvent is 3-methoxypropionitrile), then in heat-sealing film surface cover to electrode CE1, and be adsorbed with the TiO of dyestuff N3
2porous film electrode outer surface is put with aperture be the steel die of 0.4cm × 0.5cm as mask (mask), obtain DSSC T1 thus.
DSSC T1 is at 100mW/cm
2simulated solar irradiation irradiate under photoelectric current-voltage curve as shown in Figure 1.
As can be seen from Figure 1, the open-circuit photovoltage of this DSSC T1 is 0.665V, and short-circuit photocurrent is 16.18mA/cm
2, fill factor, curve factor is 0.37, and photoelectric conversion efficiency is 3.98%.
Test case 2
This test case is for illustration of the preparation of DSSC and performance test thereof.
Prepare DSSC according to the method for test case 1 and its performance tested, unlike, described to electrode CE1 with to electrode CE2 substitute, obtain DSSC T2.
DSSC T2 is at 100mW/cm
2simulated solar irradiation irradiate under photoelectric current-voltage curve as shown in Figure 1.
As can be seen from Figure 1, the open-circuit photovoltage of this DSSC T2 is 0.665V, and short-circuit photocurrent is 15.94mA/cm
2, fill factor, curve factor is 0.41, and photoelectric conversion efficiency is 4.35%.
Test case 3
This test case is for illustration of the preparation of DSSC and performance test thereof.
Prepare DSSC according to the method for test case 1 and its performance tested, unlike, described to electrode CE1 with to electrode CE3 substitute, obtain DSSC T3.
The open-circuit photovoltage of this DSSC T3 is 0.610V, and short-circuit photocurrent is 13.28mA/cm
2, fill factor, curve factor is 0.34, and photoelectric conversion efficiency is 2.75%.
As can be seen from the above embodiments, adopt method of the present invention to prepare redox graphene to electrode without the need to using toxic chemical, also without the need to the harsh conditions such as high temperature, high pressure, but the compound of graphene oxide and titanium dioxide irradiates by employing under ultraviolet light, the duplet graphene oxide utilizing titanium dioxide to inspire carries out reducing and obtaining redox graphene.Preparation method provided by the invention is easy, mild condition and environmental friendliness.In addition, described redox graphene material of the present invention can be prepared in flexible macromolecule conductive substrates, make flexible to electrode, apply more extensive.
Can be found out by the result of above-mentioned test case, the redox graphene material adopting method of the present invention to prepare can be used as DSSC to electrode material.That is, can catalytic oxidation-reduction electricity be right effectively, make DSSC normal power generation under illumination condition, and there is certain electricity conversion.Illustrate thus, the DSSC of redox graphene to electrode assembling adopting method of the present invention to prepare has good photoelectric properties, and has wide prospects for commercial application.
Claims (9)
1. a redox graphene is to the preparation method of electrode, it is characterized in that, the method comprises: by the dispersion containing graphene oxide and nano titanium oxide in conductive substrates, and the dispersant removed in the described dispersion liquid containing graphene oxide and nano titanium oxide, thus form primary membrane on described conductive substrates surface, and UV-irradiation is carried out to described primary membrane, thus obtain redox graphene film.
2. preparation method according to claim 1, wherein, the described preparation method containing the dispersion liquid of graphene oxide and nano titanium oxide comprises: graphene oxide dispersion mixed with nano titanium oxide, or graphene oxide dispersion is mixed with nano titanium oxide dispersion, obtains the dispersion liquid containing graphene oxide and nano titanium oxide.
3. preparation method according to claim 1 and 2, wherein, the concentration of described graphene oxide in the dispersion liquid containing graphene oxide and nano titanium oxide is 0.1mg/mL-1mg/mL.
4. preparation method according to claim 1 and 2, wherein, the dispersant in dispersion liquid is one or more in water, ethanol, isopropyl alcohol, dimethyl formamide and acetone, is preferably ethanol.
5. preparation method according to claim 1 and 2, wherein, the titanium dioxide granule of described nano titanium oxide to be particle diameter be 1-100nm or for thickness be the { titanium dioxide platelets of 001} crystal face of 1-100nm.
6. preparation method according to claim 1 and 2, wherein, the concentration of described nano titanium oxide in the described dispersion liquid containing graphene oxide and nano titanium oxide is 1-7 times of the concentration of graphene oxide in the dispersion liquid containing graphene oxide and nano titanium oxide, is preferably 2-5 doubly.
7. preparation method according to claim 1, wherein, the condition of UV-irradiation comprises: the wavelength of ultraviolet light is 4-380nm, and light application time is 1-12 hour, and preferably, the wavelength of ultraviolet light is 350-380nm, and light application time is 2-5 hour.
8. preparation method according to claim 1, wherein, the thickness of described conductive substrates is 0.2-3mm; Described conductive substrates be selected from mix fluorine tin dioxide conductive glass, indium tin oxide-coated glass, plating tin indium oxide PETG and plating tin indium oxide PEN in one or more.
9. the redox graphene that in claim 1-8, described in any one, method prepares is to the application of electrode in DSSC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310401152.8A CN104425135B (en) | 2013-09-05 | 2013-09-05 | Preparation method and applications of the redox graphene to electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310401152.8A CN104425135B (en) | 2013-09-05 | 2013-09-05 | Preparation method and applications of the redox graphene to electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104425135A true CN104425135A (en) | 2015-03-18 |
| CN104425135B CN104425135B (en) | 2017-08-29 |
Family
ID=52973856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310401152.8A Active CN104425135B (en) | 2013-09-05 | 2013-09-05 | Preparation method and applications of the redox graphene to electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104425135B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105002595A (en) * | 2015-07-21 | 2015-10-28 | 中国科学院宁波材料技术与工程研究所 | Polymer composite function fibers containing partial graphene, and preparation method thereof |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN105753044A (en) * | 2016-01-22 | 2016-07-13 | 浙江理工大学 | Reduced graphene oxide/titanium dioxide nanocomposite preparation method |
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN113694915A (en) * | 2021-08-25 | 2021-11-26 | 特灵空调***(中国)有限公司 | Preparation method of titanium dioxide/graphene composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011138A (en) * | 2012-11-09 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Graphene with composite pore structure, preparation method thereof and application in super capacitor |
| CN103172062A (en) * | 2013-04-17 | 2013-06-26 | 东南大学 | Preparation method of graphene film for dye-sensitized solar cell counter electrodes |
-
2013
- 2013-09-05 CN CN201310401152.8A patent/CN104425135B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011138A (en) * | 2012-11-09 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Graphene with composite pore structure, preparation method thereof and application in super capacitor |
| CN103172062A (en) * | 2013-04-17 | 2013-06-26 | 东南大学 | Preparation method of graphene film for dye-sensitized solar cell counter electrodes |
Non-Patent Citations (1)
| Title |
|---|
| GRAEME WILLIAMS等: "TiO2-Graphene Nanocomposites. UV-Assisted Photocatalytic Reduction of Graphene Oxide", 《2008 AMERICAN CHEMICAL SOCIETY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105002595A (en) * | 2015-07-21 | 2015-10-28 | 中国科学院宁波材料技术与工程研究所 | Polymer composite function fibers containing partial graphene, and preparation method thereof |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN105753044A (en) * | 2016-01-22 | 2016-07-13 | 浙江理工大学 | Reduced graphene oxide/titanium dioxide nanocomposite preparation method |
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN113694915A (en) * | 2021-08-25 | 2021-11-26 | 特灵空调***(中国)有限公司 | Preparation method of titanium dioxide/graphene composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104425135B (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sönmezoğlu et al. | High-efficiency dye-sensitized solar cells using ferrocene-based electrolytes and natural photosensitizers | |
| CN100511718C (en) | Nanometer oxide porous membrane electrode and preparing method and application thereof | |
| CN104425135A (en) | Preparation method for reduced graphene oxide counter electrode and application thereof | |
| CN101901693A (en) | Graphene composite dye-sensitized solar cell light anode and preparation method thereof | |
| CN102074373B (en) | Dye-sensitized solar battery light anode and preparation method thereof | |
| CN107221441A (en) | A kind of solar cell based on composite nanostructure light anode | |
| Xu et al. | A new in-situ preparation method to CuS electrodes for CdS/CdSe co-sensitized solar cells | |
| CN104992843B (en) | A kind of titanium disulfide nanometer sheet/graphene composite material is to electrode and preparation method thereof | |
| CN103165287B (en) | Photocuring prepares the method for Nano-titania Porous Films | |
| Kusumawati et al. | TiO2/graphene nanocomposite layers for improving the performances of dye-sensitized solar cells using a cobalt redox shuttle | |
| CN104465113A (en) | Nitrogen-doped graphene counter electrode preparing method and application of nitrogen-doped graphene counter electrode in dye-sensitized solar cell | |
| Wang et al. | The feasible photoanode of graphene oxide/zinc aluminum mixed metal oxides for the dye-sensitized solar cell | |
| Abrol et al. | Fabrication of DSSC using doctor blades method incorporating polymer electrolytes | |
| CN103594249B (en) | A kind of graphene oxide-nano-graphite flour complexes is to the preparations and applicatio of electrode | |
| CN105977035A (en) | Dye-sensitized solar cell of novel electrode structure | |
| CN101572190B (en) | Method for preparing TiO2 slurry of organic carrier system | |
| Li et al. | Nanofabrication of uniform and stabilizer-free self-assembled platinum monolayers as counter electrodes for dye-sensitized solar cells | |
| CN100541822C (en) | DSSC of a kind of nano-crystal film and preparation method thereof | |
| CN103714976B (en) | A kind of used by dye sensitization solar battery Cu3SnS4Nano material is to electrode and preparation method thereof | |
| Cao et al. | Graphene/zinc aluminum mixed metal oxides photo anode for CdS quantum dot-sensitized solar cell | |
| CN115064388A (en) | Dye-sensitive solar cell based on composite structure photo-anode and preparation method and application thereof | |
| CN104681283A (en) | Modified carbon black and graphite counter electrode as well as preparation method and application thereof | |
| Hu et al. | Fabrication of quantum dot sensitized solar cells based on transparent TiO2 photoanodes | |
| Gao et al. | Submicrometer@ nano bimodal TiO2 particles as easily sintered, crack-free, and current-contributed scattering layers for dye-sensitized solar cells | |
| Li et al. | Fabrication of CdSe/CdTe quantum dots co-sensitized TiO2 nanorods by electrochemical atomic layer deposition method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |