CN104412335A - Hybrid electrode using silver nanowires and graphene, and preparation method thereof - Google Patents

Hybrid electrode using silver nanowires and graphene, and preparation method thereof Download PDF

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CN104412335A
CN104412335A CN201380035160.3A CN201380035160A CN104412335A CN 104412335 A CN104412335 A CN 104412335A CN 201380035160 A CN201380035160 A CN 201380035160A CN 104412335 A CN104412335 A CN 104412335A
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preparation
graphene
transparent mixed
nano silver
silver wire
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CN104412335B (en
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金性龙
李志勋
阿尔-马蒙·***
印仁植
高英姬
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Industry Academic Cooperation Foundation of KNUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/0224—Electrodes
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • Y02E10/549—Organic PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a hybrid electrode using silver nanowires and graphene, and a preparation method thereof, and more specifically, provides: a hybrid electrode comprising a silver nanowire network and graphene so as to have high light transmittance, improved surface resistance and electrocatalytic reactivity, and flexibility; and a preparation method thereof.

Description

Utilize mixed electrode of nano silver wire and Graphene and preparation method thereof
Technical field
The present invention relates to mixed electrode utilizing nano silver wire and Graphene and preparation method thereof, in detail, relate to the technology of the mixed electrode providing following and preparation method thereof: above-mentioned mixed electrode comprises silver nanoparticle gauze and Graphene, thus the light transmittance of above-mentioned mixed electrode is high, above-mentioned mixed electrode has sheet resistance and the flexibility of raising.
Background technology
In display device or solar cell, make Transmission light and transmitting image the transparency electrode that electric current occurs is core component.At present, using maximum is tin indium oxide (indium tin oxide; ITO) as transparency electrode purposes.
But the use amount of tin indium oxide significantly increases year by year, the reserves of corresponding tcrude ore are abundant not, thus estimate that corresponding tcrude ore can be exhausted soon, and the price of the tin indium oxide of costliness become very large problem.And, when making to be bent by the transparency electrode of the such as Preparation of tin indium oxide, there is slight crack or fragmentation in sull, therefore, the problem that the sheet resistance (sheet resistance) that there is transparency electrode increases, and existence is difficult to the shortcoming being applicable to flexible electronic device.Therefore, the transparency electrode of problem as above can be solved in the urgent need to exploitation.
Be applied in American Chemical Society's nanometer (ACS Nano, 2010,4,2955)) in the problem occurring having the particle of insulating properties with the surface that transparency electrode prepared by nano silver wire exists nano silver wire that proposes.The flexible electrode of the nano silver wire of the sheet resistance that use in the past has and oxide-based transparency electrode is similar needs high critical concentration because of the non-conductive portion existed between mutually stacked nano wire, therefore, the electrode only formed by pure nano silver wire film is difficult to be applicable to display or solar cell.
As everyone knows, the critical concentration of silver nanoparticle gauze successfully can be changed by the diameter and length regulating nano wire.The nano wire with the structure of mutually crossing has the structure of sparse thin separation, thus there is the problem that electricity cannot flow equably in whole.Further, there is the shortcoming with insulating property (properties) in film or the coating with the mutually stacked structure of nano silver wire, therefore, there is the problem of electrical property or the catalysis characteristics that cannot have needed for electronic equipment.
Can be used alone nano silver wire to have the sheet resistance similar with transparency electrode in the past, but, because of be formed at the surface of nano silver wire silver oxide insulating particle and occur in use procedure sheet resistance increase problem.And, in the structure of silver nanoparticle gauze, there is the idle space (uncovered area) generated because nano silver wire mutually crosses, therefore there is the insulating space that electronics cannot be made to pass through, the critical concentration of high nano silver wire is needed thus in order to have high conductivity, cause the making of electronic equipment or electrode used for solar batteries to have problems, the film formed by the net of nano silver wire has high rough surface group, thus there is the problem causing electronic installation short circuit.
Further, in utilizing carbon nano-tube just to carry out to the research preparing electrode, but the electrode pair moisture prepared by carbon nano-tube is very sensitive, if absorb moisture, sheet resistance can significantly increase, and in order to prevent this phenomenon, and existence needs the problem of carrying out external application.Further, different from nano silver wire, the structure of carbon nano-tube is sinuate, is thus difficult to the coacervation avoiding occurring mutually being wound around serious carbon nano-tube.
The work function of electrode is one of most important factor in the electronic device.In transparent conductive electrode, Graphene is used to be the electron transmission ability of Graphene and the catalysis characteristics of Graphene as the object of work function Auto-regulator.
The resistance of the touch screen electrode used in smart mobile phone or touch screen is 100-500 Ω/sq, and the resistance of the electrode used in the photoelectronic device of such as solar cell is 10 ~ 30 Ω/sq, even if with the low metal oxide of resistance.Usually, utilize transmissivity in 550nm be more than 90% tin indium oxide (indium tin oxide) or transmissivity lower than tin indium oxide but be more than 80% fluorine-doped tin oxide (FTO, fluorine-doped tinoxide) as electrode material.
But these electrode materials are unstable in acid or alkali, ion is easy to polymeric membrane diffusion and infiltration, and the transmissivity near infrared range is low, and the problem of fragmentation fluorine-doped tin oxide exists the leakage of current, bending during because of structural defect.
Further, the platinum that the comparative electrode of solar cell uses electrocatalytic reaction (electrocatalytic activity) outstanding usually, but there is expensive problem in platinum.
Therefore, the exploitation of photoelectron device must develop the new electrode materials of the high conductivity that chemical stability is outstanding, flatness is outstanding, transmissivity is high, has carried out the research much carrying out the electrode material of alternative platinum, tin indium oxide, fluorine-doped tin oxide etc. about use carbon nano-tube, graphite, conductibility macromolecule, carbon black etc.
After 2004 find, the Graphene with a Rotating fields of graphite with two-dimensional shapes shows the outstanding characteristic that can be applied to following photoelectron device, therefore just carries out a lot of correlative study to Graphene.Especially, the semiconductor of Graphene to be band gap be 0eV, the conduction band of Graphene and valence band (valence band) contact with each other, thus there is unique character, and, the work function (4.42eV) of Graphene is close with the fluorine-doped tin oxide (4.40eV) being used as transparency electrode, carries out the application study of electrode and optoelectronic areas because of the conductivity high in theory of Graphene and cheap processing possibility.
In dye-sensitized solar cell or organic solar batteries, utilize the transparency electrode applied by fluorine-doped tin oxide or tin indium oxide in a large number, but the performance of the roughness of electrode to photoelectron device is fatefulue.The electric short circuit of solar cell can be caused in the coarse surface of fluorine-doped tin oxide electrode, the graphene film that therefore intended surface is very level and smooth can the possibility of replacement fluorine doped stannum oxide very high.Further, the operation that substrate applies fluorine-doped tin oxide is very complicated, uses expensive evaporation or sputtering process, therefore, causes the price of fluorine-doped tin oxide electrode to rise, thus needs exploitation can the technology of replacement fluorine doped stannum oxide.
So far, according to the content of Graphene, the conductivity of transparent graphene composite material is 10 -3~ 1S/cm degree, thus cannot be used as the electrode material of photoelectron device.
Summary of the invention
the technical problem to be solved in the present invention
The object of the invention is to, there is provided following mixed electrode and preparation method thereof: above-mentioned mixed electrode comprises silver nanoparticle gauze and Graphene, thus the light transmittance of above-mentioned mixed electrode is high, above-mentioned mixed electrode has the sheet resistance of raising, electrocatalytic reaction and flexibility.
technical scheme
In order to reach above-mentioned purpose, the feature of the mixed electrode of one embodiment of the invention is, comprises substrate, nano silver wire and graphene film.
On the other hand, in order to reach above-mentioned purpose, the feature of the preparation method of the mixed electrode of one embodiment of the invention is, comprising: the step of silver coating nano wire on substrate; And on the substrate being coated with above-mentioned nano silver wire, apply the step of solution-type Graphene.
Further, in order to reach above-mentioned purpose, the feature of the preparation method of the mixed electrode of another embodiment of the present invention is, comprising: the step of silver coating nano wire on substrate; The substrate being coated with above-mentioned nano silver wire applies the step of lysotype graphene oxide; And the step that above-mentioned graphene oxide is reduced.
beneficial effect
It is high and have the sheet resistance of raising and the effect of flexibility that mixed electrode of the present invention has light transmittance.
Further, the hot stability of chemistry of mixed electrode of the present invention is outstanding, can be applicable to the electrode of the various electronic equipments such as dye-sensitized solar cell.
Embodiment
Below, mixed electrode of the present invention and preparation method thereof is described in detail.
Mixed electrode
The invention provides the mixed electrode comprising substrate, nano silver wire and graphene film.
Wherein, as long as the transparent and material with flexibility of aforesaid substrate does not just limit, especially, aforesaid substrate is preferably selected from PETG (PET, Polyethylene Terephthalate), polyether sulfone (PES, Poly Ether Sulfone), polymethyl methacrylate (PMMA, Poly Methyl Methacrylate), Merlon (PC, Poly Carbonate), PEN (PEN, Polyethylene Naphthalate), cyclic olefine copolymer (COC, Cyclic Olefin Copolymer), polyimides (PI, Poly Imide) in more than one.
Preferably, the length of the above-mentioned nano silver wire included by mixed electrode of the present invention is 5 μm ~ 150 μm and aspect ratio is 200 ~ 2500:1.The sheet resistance of the effect length electrode of nano silver wire and light transmittance, therefore, under the length of above-mentioned nano silver wire is less than 5 μm of situations, need the nano silver wire of more, and, the quantity of the contact point mutually crossing along with nano silver wire and nano silver wire and generate increases, final problem sheet resistance occurring and increases.When the length of nano silver wire is greater than 150 μm, there is the problem that reproducibility declines, processability worsens of sheet resistance.
Preferably, the concentration of the above-mentioned nano silver wire included by mixed electrode of the present invention is 1.0 ~ 10mg/mL.The concentration of nano silver wire affects the light transmittance of electrode and the factor of sheet resistance, therefore, when the concentration of above-mentioned nano silver wire is less than 1.0mg/mL, viscosity because of nano silver wire solution is too low and cause coating uniformity to decline, when the concentration of nano silver wire is greater than 10mg/mL, there is the problem being difficult to carry out applying because viscosity is too high.
Preferably, the Graphene used in the preparation process of mixed electrode of the present invention or the concentration of graphene oxide solution are 0.5 ~ 5.0mg/mL.When the concentration of graphene solution is less than 0.5mg/mL, need nozzle is is repeatedly come and gone while carry out applying or carry out to repeat coating to obtain required sheet resistance, therefore there is the problem needing the coating time grown very much, when the concentration of graphene solution is greater than 5.0mg/mL, stacked more than 10 layers and thickening situation is more of the graphene film of dispersion, thus exists that surface roughness is high, the problem of light transmittance decline.
Further, preferably, the thickness of the graphene film of coating is 1 ~ 100nm.When the thickness of graphene film is greater than 100nm, the surface roughness because of coating high and can limit use be electrode applications.
The electrode of mixed electrode of the present invention to be sheet resistance be 10 ~ 500 Ω/sq, conductivity is outstanding, and light transmittance is 70 ~ 92%, transparent, thus effectively can be used in dye-sensitized solar cell etc. and need the electronic equipment of the transparency and solar cell etc.
The preparation method of mixed electrode
The invention provides a kind of preparation method of mixed electrode, the preparation method of above-mentioned mixed electrode comprises: the step of silver coating nano wire on substrate; And on the substrate being coated with above-mentioned nano silver wire, apply the step of solution-type Graphene.
Further, according to another embodiment of the present invention, provide a kind of preparation method of mixed electrode, the preparation method of above-mentioned mixed electrode comprises: the step of silver coating nano wire on substrate; The substrate being coated with above-mentioned nano silver wire applies the step of lysotype graphene oxide; And the step that above-mentioned graphene oxide is reduced.
Wherein, as long as the transparent and material with flexibility of aforesaid substrate does not just limit, especially, aforesaid substrate is preferably selected from more than one in PETG (PET), polyether sulfone (PES), polymethyl methacrylate (PMMA), Merlon (PC), PEN (PEN), cyclic olefine copolymer (COC), polyimides (PI).
Preferably, the length of the above-mentioned nano silver wire included by mixed electrode of the present invention is 5 μm ~ 150 μm and aspect ratio is 200 ~ 2500:1.The sheet resistance of the effect length electrode of nano silver wire and light transmittance, therefore, under the length of above-mentioned nano silver wire is less than 5 μm of situations, need the nano silver wire of more, and, the quantity of the contact point mutually crossing along with nano silver wire and nano silver wire and generate increases, final problem sheet resistance occurring and increases.When the length of nano silver wire is greater than 150 μm, there is the problem that reproducibility declines, processability worsens of sheet resistance.
Preferably, the concentration of the above-mentioned nano silver wire included by mixed electrode of the present invention is 1.0 ~ 10mg/mL.The concentration of nano silver wire affects the light transmittance of electrode and the factor of sheet resistance, therefore, when the concentration of above-mentioned nano silver wire is less than 1.0mg/mL, viscosity because of nano silver wire solution is too low and cause coating uniformity to decline, when the concentration of nano silver wire is greater than 10mg/mL, there is the problem being difficult to carry out applying because viscosity is too high.
Preferably, the Graphene used in the preparation process of mixed electrode of the present invention or the concentration of graphene oxide solution are 0.5 ~ 5.0mg/mL.When the concentration of graphene solution is less than 0.5mg/mL, need nozzle is is repeatedly come and gone while carry out applying or carry out to repeat coating to obtain required sheet resistance, therefore there is the problem needing the coating time grown very much, when the concentration of graphene solution is greater than 5.0mg/mL, stacked more than 10 layers and thickening situation is more of the graphene film of dispersion, thus exists that surface roughness is high, the problem of light transmittance decline.
Further, preferably, the thickness of the graphene film of coating is 1 ~ 100nm.When graphene film thickness be greater than 100nm, the surface roughness because of coating high and can limit use be electrode applications.
The method of method or coating lysotype graphene oxide that the substrate being coated with nano wire applies solution-type Graphene can utilize the multiple methods such as vacuum filtration process, gunite, ink-jet method, spin-coating method.
In the preparation method of the present invention utilizing reduction process, method of reducing can be divided into 1) utilize reductant solution to process the method for graphene oxide; And 2) utilize volatile reducing-agent steam to process two kinds of methods such as the method for graphene oxide.
Wherein, as long as the material that above-mentioned reductant solution can make graphene oxide reduce just does not limit, but preferably, above-mentioned reductant solution is for being selected from more than one of hydrazine, thionyl chloride (thionyl chloride) and sodium borohydride.
On the other hand, the boiling point of above-mentioned reducing agent steam is 10 ~ 200 DEG C, preferably, above-mentioned reducing agent steam be selected from hydrazine monohydrate, sodium borohydride, quinhydrones, dimethylhydrazine, phenylhydrazine, ethylenediamine more than one.
Below, by specific embodiment, mixed electrode of the present invention and preparation method thereof is described.
Preparation example
(1) preparation of nano silver wire
As in ACS Nano (American Chemical Society's nanometer, 2010,4 (5), 2955)) in the method introduced, use polyalcohol to regulate diameter and length, synthesis of silver nano-wire thus.
Particularly, the polyvinylpyrrolidone (PVP) of 6.010mmol and the KBr (KBr) of 84.032mmol are put into the round-bottomed flask of the ethylene glycol (EG) that 20mL is housed, and synthesize.
In order to thermostabilization, heat at the temperature of 170 DEG C after one hour while stirring the mixture with 800rpm (revolutions per minute), add the AgCl powder of 0.349mmol, generate initial stage Ag crystallization (seed) thus.After five minutes, by the liquor argenti nitratis ophthalmicus in the ethylene glycol of 1.295mmol with 1mL/min titration ten minutes, and utilize nano silver wire was grown completely in 1 hour.
By mixture instantaneous cooling to about 5 DEG C, and maintain 50 minutes at normal temperature.Use water and acetone, utilize continuous print to disperse-precipitate circulation purification product.After the dispersions of 15 times-precipitation circulation, most nano particle is removed in the process pouring (decantation) container into.
The accessory substance at initial stage is nano wire, nanometer rods, nanocube.In order to remove nanocube, nanometer rods and other nano particles, and employ polycarbonate membrane filter.Nano silver wire on polycarbonate membrane is devoted carrene to dissolve to make Merlon, obtain elongated nano wire thus.The nano wire block of cohesion easily can be scattered in multi-solvents, and the ultrasonic wave of short time is also abundant.In order to control the length of nano silver wire, change polyvinylpyrrolidone (PVP) and AgNO 3ratio.
(2) preparation of graphene oxide
As everyone knows, Graphene has the structure that carbon atom is formed by two-dimentional covalent bond, and has the strong catalytic activity (catalytic activity) of unique character.The preparation method of graphene film makes highly oriented pyrolytic graphite (HOPG, highly ordered pyrolytic graphite) repeatedly peel off (peeling) to carry out interlaminar separation and the mechanical methods be prepared and the method etc. prepared by being chemically oxidized of carbon element.
In an embodiment of the present invention, utilize the top-down solution operation being easy to prepare to make graphite oxidation, and utilize the graphene oxide prepared thus to prepare Graphene.The preparation method of graphene oxide is as follows.
Graphite as the material that sets out of Graphene employs the flake graphite purchased from Bay Carbon Co., and utilizes Hummers (Xiu Mosi) method to prepare graphene oxide.
Prepare graphene oxide by bronsted lowry acids and bases bronsted lowry process cause graphite, utilize sulfuric acid and potassium permanganate (KMnO 4) between graphite flake, import oxide, and pH is adjusted to neutral rear use.
Potassium sulfate is utilized to purify to methyl alcohol under nitrogen flowing.3-aminopropyltriethoxysilane (APTES), concentrated hydrochloric acid equal solvent and reagent, purchased from aldrich (Aldrich) company, are purified.
Graphite (2g) is put into the flask of 500ml, and place 10 minutes in sulfuric acid (50ml) ice container.Potassium permanganate (6g) is added, each interpolation a small amount of (attention is no more than 25 DEG C) to its mixing material.Afterwards, react two hours at the temperature of 35 DEG C.After the reaction of two hours, add distilled water (92ml) and react 15 minutes again.
Then add distilled water (280ml) and hydrogen peroxide (10ml) reacts 10 minutes then.Then, after interpolation distilled water (900ml) and hydrochloric acid (100ml) react 30 minutes, utilize distilled water to clean, until become pH7, and carry out drying in vacuum drier.By the ultrasonic wave operation of 60W, graphite is carried out to the interlaminar separation of at least 3 hours.High purity oxygen functionalized graphene is obtained from separated upper solution by evaporization process.
Although the graphene oxide obtained by above operation is non-conductive material, being through reduction process will become Graphene, and has transport properties.The reactive group comprising the oxygen be present in graphene oxide is given hydrophily base and is also given the characteristic dissolved easily in water, therefore, when preparing Graphene, extremely important in a large amount of production and INDUSTRIAL APPLICABILITY.In an embodiment of the present invention, centrifugal separation, freeze-dried method is employed to obtain high-purity graphene oxide to improve the purity of graphene oxide.
(3) preparation of mixed electrode and the reduction of graphene oxide
In an embodiment of the present invention, in order to utilize solution based processes to employ spin coating operation to prepare Graphene electrodes.
In order to utilize spin coating operation to form uniform graphene oxide film on substrate, and graphene oxide disperseed and regulates the concentration etc. of spin coating rotating speed and graphene oxide, and being purged by non-reactive gas, obtaining film thus.
While change the experiment factor of spincoating conditions etc., utilize flying-spot microscope or atomic force microscope to the size variation of the dispersity and graphene oxide of observing graphene oxide, select the best spincoating conditions prepared needed for electrode thus.Further, in the present invention, after graphene oxide be impregnated in hydrazine solution, utilize spin-coating method online to be coated on nano silver wire, prepare mixed electrode thus.
Be spun in the graphene oxide on nano silver wire and be attached with a lot of epoxy radicals, hydroxyl, carboxyl etc., therefore, have electrical insulating property, therefore itself cannot be used as electrode material.Need reduction process graphene oxide being converted to graphene-structured, use following reduction process.
The graphene oxide solution being stably scattered in water is spun on and is coated with on the substrate of nano silver wire, and carry out the chemically heat treatment of 10 minutes at the temperature of 150 DEG C after, utilize hydrazine gas to reduce.High sheet resistance (the > 10 of graphene oxide 10Ω/sq) in the mixed electrode of nano wire and Graphene, the value of 100 Ω/below sq is dropped to by reduction process.
(4) mixed electrode is applicable to dye-sensitized solar cell
The mixed electrode of nano silver wire and the Graphene obtained in the present invention is utilized to come replacement fluorine doped stannum oxide or tin indium oxide as electrode to prepare dye-sensitized solar cell.
The present invention can substitute indium tin oxide material exhausted within the more than ten years, infinitely can be applied to the multiple optoelectronic areas such as solar cell, touch screen.And, the mixed electrode utilizing the nano silver wire of solution-type and Graphene to prepare utilizes abundant carbon resource and nano silver wire, therefore compared with tin indium oxide or fluorine-doped tin oxide, prepare low cost, there is crack with tin indium oxide or fluorine-doped tin oxide when bending and increase compared with sheet resistance, after bending experiment repeatedly, surface electrode does not almost change yet, and therefore has the advantage that can be applicable to flexible apparatus.
< embodiment 1>
The graphene solution of reduction is applied on the net to prepare mixed electrode at nano silver wire.
Particularly, utilize Mei Yueer (Meyor) bar that diameter is about 35nm and the nano silver wire solution that length is about 30 μm is coated on PETG (PET) base material, and drying is carried out to nano silver wire film.Graphene oxide be impregnated in hydrazine solution to be reduced into Graphene.With the rotating speed of 1000rpm, the graphene solution of reduction is spun on nano silver wire nethike embrane.The thickness of the graphene film of external application (overcoat) can be changed by adjusting rotary speed.When rotating speed is 1000rpm, sheet resistance reaches 165 Ω/sq, and light transmittance reaches 81%.
In the nano silver wire with the web frame mutually crossed, nano wire cannot a part of region of covering substrates, is thus formed " inactive area (the uncovered area) " with non-conducting character.Cannot cover the region overlay graphene film of whole base material as above, thus, transparency electrode has electrical connectivity on the whole.
< embodiment 2>
Utilize the method identical with embodiment 1, but prepared by the order of modification layer.Namely on base material, first apply the Graphene of reduction, and silver coating nano wire thereon.
< embodiment 3>
Utilize original position (in-situ) reducing process that the graphene oxide spread on nano silver wire is prepared into mixed electrode outward.
Particularly, on PETG (PET) base material, utilize Mei Yueer (Meyor) bar that diameter is about 35nm and after the nano silver wire solution that length is about 30 μm carries out nano silver wire coating, thereon with 1000rpm spin coating graphene oxide.Utilize the mixed film of hydrazine (hydrazine) steam treated drying.Acquired sheet resistance is 150 Ω/sq, and light transmittance is 84%.Nano silver wire-graphene oxide mixed structure is exposed to hydrazine steam, then realizes the reduction of original position (in-situ) graphene oxide, meanwhile, hydrazine steam makes the silver salt reduction being present in nano silver wire.
< comparative example 1>
The preparation method of nano silver wire electrode is as follows.
Use polyol process (polyol method) to synthesize diameter and be about 35nm and length is about the nano silver wire of 30 μm.For PET substrate, utilize 3-aminopropyltriethoxysilane (APTES) to process, and utilize the power of 50W to carry out oxygen plasma treatment.Preparation concentration is the nano silver wire dispersion liquid of 5mg/mL.Mei Yueer (Meyor) bar is utilized to be coated on PET substrate by nano silver wire solution, drying 10 ~ 30 minutes at the temperature of 150 DEG C.The sheet resistance of nano silver wire film is 175 Ω/sq, is about 83% at the light transmittance of the wavelength of 550nm.
< comparative example 2>
The preparation method of the combined silver nano wire used in embodiment 1 and the electrode of water-soluble fibre is as follows.
Use water-soluble cellulose (such as, hydroxypropyl methylcellulose (HPMC), methylcellulose, hydroxyethylcellulose etc.) as viscosity modifier, use xanthans (Xanthan gum) as surfactant, use polyvinyl alcohol as processing aid.Viscosity modifier plays and improves coating processability but the effect not affecting the character of silver nanoparticle gauze.
< comparative example 3>
Prepare the mixed electrode formed by single wall carbon nano tube and Graphene.As the content recorded in US2007/0284557, admixed graphite alkene and carbon nano-tube apply the mixed transparent electrode formed by graphene-carbon nano tube.The diameter of the single wall carbon nano tube used is about 6nm, and length is about 200nm.The Graphene used in this comparative example is the simple layer similar with the Graphene mentioned at PNAS (institute of American Academy of Sciences reports, vol.102, No.30 (2005)) or multi-layer graphene.Because single wall carbon nano tube is between graphene film and graphene film, the loose contact thus between graphene film, the quantity of the contact that graphene film contacts with each other increases, and therefore, sheet resistance is high to about 2000 Ω/sq, and light transmittance is 80%.
As compared to the electrode formed by carbon nano-tube and Graphene, the mixed transparent electrode formed by nano silver wire and Graphene has better connectivity and lower sheet resistance value.
< comparative example 4>
Be present in the transparency electrode of the metal oxide on the surface of nano silver wire utilizing salt acid vapour to eliminate, the metal impurities being present in the surface of nano silver wire make sheet resistance sharply increase along with the process of time.As described in the patent in the past of US2008/0286447A1, comprise the organic anticorrisive agent (such as, fragrant triazole, imidazoles, thiazole) of N and S to protect nano silver wire to use.Propose at Nanoscale Research Letters (research in nanotechnology news flash, 2011,6,75) metal oxide utilizing salt acid vapour to remove the surface of silver nanostructured thing and can reduce sheet resistance.In US2011/0024159, utilize ammonia to clean from unreacted AgNO 3the silver halide (Silver halide) obtained and other accessory substances.Ammonia can with insoluble silver salt Composite, finally utilize water to clean.The reduction of hydrazine steam to silver-colored graphene oxide is effective.
Evaluate
The structure transitivity arranging comparative example and embodiment is able to following table 1 and table 2.
Table 1
Table 2
(◎: very outstanding, zero: outstanding, ×: bad)
With reference to table 1 and table 2 known, embodiment 1 to embodiment 3 is compared with comparative example 1, comparative example 2, comparative example 4, and electro catalytic activity is outstanding, and compared with embodiment 3, ageing stability is outstanding.
Above, specific embodiments of the invention are illustrated, but, can various deformation be carried out without departing from the scope of the present invention.Therefore, scope of the present invention is not limited to illustrated embodiment, but determines according to the claimed scope of invention and equivalent substituting thereof.
As mentioned above, with reference to limited embodiment and illustrate the present invention, but the present invention is not limited to above-described embodiment, and one skilled in the art of the present invention can carry out multiple amendment and distortion based on as above record.Therefore, thought of the present invention should according to invention claimed scope and defining, and should be interpreted as inventing the equivalent of claimed scope or equivalent variations all belongs to thought range of the present invention.

Claims (14)

1. a transparent mixed electrode, is characterized in that,
Comprise substrate, nano silver wire and graphene film;
The length of described nano silver wire is 5 μm ~ 150 μm, and aspect ratio is 200 ~ 2500:1, and the sheet resistance of described transparent mixed electrode is 10 ~ 500 Ω/sq.
2. transparent mixed electrode according to claim 1, it is characterized in that, described substrate be selected from PETG, polyether sulfone, polymethyl methacrylate, Merlon, cyclic olefine copolymer, PEN and polyimides more than one.
3. transparent mixed electrode according to claim 1, is characterized in that, the thickness of described graphene film is 1 ~ 100nm.
4. transparent mixed electrode according to claim 1, is characterized in that, the light transmittance of described transparent mixed electrode is 70 ~ 94%.
5. a preparation method for transparent mixed electrode, is characterized in that, comprising:
The step of silver coating nano wire on substrate, and
The substrate being coated with described nano silver wire applies the step of solution-type Graphene;
The length of described nano silver wire is 5 μm ~ 150 μm, and aspect ratio is 200 ~ 2500:1, and the sheet resistance of described transparent mixed electrode is 10 ~ 500 Ω/sq.
6. the preparation method of transparent mixed electrode according to claim 5, it is characterized in that, described substrate be selected from PETG, polyether sulfone, polymethyl methacrylate, Merlon, cyclic olefine copolymer, PEN and polyimides more than one.
7. the preparation method of transparent mixed electrode according to claim 5, is characterized in that, the concentration of described nano silver wire is 1.0 ~ 10mg/mL.
8. a preparation method for transparent mixed electrode, is characterized in that, comprising:
The step of silver coating nano wire on substrate,
The substrate being coated with described nano silver wire applies the step of lysotype graphene oxide, and
Make the step that described graphene oxide reduces;
The length of described nano silver wire is 5 μm ~ 150 μm, and aspect ratio is 200 ~ 2500:1, and the sheet resistance of described transparent mixed electrode is 10 ~ 500 Ω/sq.
9. the preparation method of transparent mixed electrode according to claim 8, is characterized in that, described reduction utilizes reductant solution to process graphene oxide.
10. the preparation method of transparent mixed electrode according to claim 9, is characterized in that, described reductant solution is be selected from more than one of hydrazine, thionyl chloride and sodium borohydride.
The preparation method of 11. transparent mixed electrodes according to claim 8, is characterized in that, described reduction utilizes volatile reducing-agent steam to process graphene oxide.
The preparation method of 12. transparent mixed electrodes according to claim 11, it is characterized in that, the boiling point of described reducing agent steam is 10 ~ 200 DEG C, described reducing agent steam be selected from hydrazine monohydrate, sodium borohydride, quinhydrones, dimethylhydrazine, phenylhydrazine, ethylenediamine more than one.
The preparation method of 13. transparent mixed electrodes according to claim 8, it is characterized in that, described substrate be selected from PETG, polyether sulfone, polymethyl methacrylate, Merlon, cyclic olefine copolymer, PEN and polyimides more than one.
The preparation method of 14. transparent mixed electrodes according to claim 8, is characterized in that, the concentration of described nano silver wire is 1.0 ~ 10mg/mL.
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