CN206271561U - Graphene-based laminated film and automatically cleaning solar film battery - Google Patents

Abstract

The utility model provides a kind of graphene-based laminated film and automatically cleaning solar film battery, vertical-growth goes out continuous Nanometer Thin Films by Sol-Gel Method on graphene film, during using the laminated film as light transmission layer, the high transmittance of graphene film ensure that higher light transmission rate of the laminated film as light transmission layer, and self-cleaning function is realized using Nanometer Thin Films by Sol-Gel Method；Further, using the graphene-based laminated film as electrode layer, conduction rate is improved using the quick carrier mobility of graphene film, reduce loss of the battery in opto-electronic conversion, by the use of the nano thin-film perpendicular to graphene film as dye migration passage, improve dye migration speed, and then improve generating efficiency.

Description

Graphene-based laminated film and automatically cleaning solar film battery

Technical field

The utility model is related to technical field of semiconductors, and in particular to a kind of graphene-based laminated film and the automatically cleaning sun Can hull cell.

Background technology

With the development and the continuous reduction of technology node of semiconductor technology, traditional silicon materials have shown many limits System and defect, because Graphene is a kind of current most strong novel nano material of most thin, intensity highest, electrical and thermal conductivity performance in the world Material, so Graphene turns into the substitute of preferable silicon.Prepared by graphene film and performance has been subjected to global concern With it is widely studied, graphene film is expected to be applied to because with quick carrier mobility, high rigidity and flexibility In semiconductor devices.

However, the energy gap of Graphene is zero, and semi-conducting material is requirement has certain energy gap, therefore is ground Study carefully and how the above-mentioned advantage of graphene film is applied in semiconductor applications be significant.Generally semiconductor is received Rice material and Graphene to be combined and have the composite construction that the above-mentioned advantage of Graphene also has semiconducting behavior concurrently concurrently preparing, however, Growth of the semiconductor nano material on Graphene is more difficult, and this is also the problem of industry；Although someone is in Graphene Continuous nano material film is prepared on film, but these nano material films are easy to come off, and limit the composite junction The application of structure；In order to improve the conjugation of nano material film and graphene film, can attempt thin using nano material is reduced The method of the thickness of film, and nanometer is played in order to further grow continuous nano material film on graphene film The performance of material film and flexibility of graphene-based composite construction etc. is improved, be more desirable to be grown on graphene film receives The thickness of rice material film is reduced to ultra-thin or even several nanometer of thickness, but it is thin so to cannot get continuous nano material Film.

Additionally, there is following defect in existing solar cell：Solar cell causes itself in air for a long time Cleaning problems, and light utilization efficiency is relatively low, and generating efficiency is low, volume is larger, and solar cell can not become according to external environment Effectively self-protection is accomplished in change.For example, when the rainy day is run into, solar cell is exposed among rainwater, when in night, Solar cell can not now absorb sunshine and be operated and be also exposed in air, so as to cause the dirt of solar cell Dye and service life reduction.Therefore, on the premise of the transmitance for not influenceing solar cell, improve generating efficiency can also make for research Solar cell has self-cleaning function concurrently, is significant.

Utility model content

In order to overcome problem above, the utility model aims to provide a kind of graphene-based laminated film and with the Graphene Solar film battery based on based coextruded film causes to grow very thin continuous nano material on the graphene film Film, and can also improve generating efficiency while making solar film battery that there is self-cleaning function.

In order to achieve the above object, a kind of graphene-based laminated film of the utility model, it is characterised in that including：One stone Black alkene film and vertical-growth are in the nano thin-film on the graphene film；The plane of the nano thin-film and the graphite Alkene film normal；The bottom of the nano thin-film is mutually bonded with the graphene film by chemical bond；The nano thin-film Material is conductor photocatalysis material.

Preferably, the graphene film is that the graphene film of two-layer atomic layer or the Graphene of three layers of atomic layer are thin Film.

Preferably, the nano thin-film has multiple micro- engraved structures, so as to constitute nano net.

Preferably, the spacing between adjacent described micro- engraved structure is not more than 10nm.

Preferably, the nano net is grown by nano wire perpendicular to transparent substrates and the side of adjacent nanowires is in contact shape Into nano thin-film, then etch to form micro- void region through nano thin-film.

Preferably, mutually it is bonded by chemical bond between the nano wire being in contact.

Preferably, the diameter of nano wire is the thickness of the nano thin-film.

Preferably, the thickness of the nano thin-film is not more than 10nm.

Preferably, the conductor photocatalysis material is wide band gap semiconducter catalysis material.

Preferably, the wide band gap semiconducter catalysis material is titanium alloy nano line and/or zinc alloy nano-wire.

Preferably, there are multiple nano thin-films being arranged in array on the graphene film.

In order to achieve the above object, the utility model additionally provides a kind of graphene-based automatically cleaning solar film battery, It is disposed with light transmission layer, transparent electrode layer and light conversion layer from top to bottom, and incident light is successively through light transmission layer and thoroughly Prescribed electrode layer, enters back into light conversion layer, and light conversion layer carries out opto-electronic conversion and produce electricity after absorbing incident light；Light transmission layer With above-mentioned graphene-based laminated film, wherein, the bottom of the graphene film is located at transparent electrode layer upper surface.

Preferably, the transparent electrode layer uses the graphene-based laminated film described in claim 1, in light transmission layer The contact of graphene film lower surface is provided with transparent substrate, the graphene film close-fitting transparent substrate layer following table of transparent electrode layer Face, the nano thin-film in the graphene-based laminated film of transparent electrode layer is located at the lower surface of its graphene film.

Preferably, scalable flexible and transparent protective layer is provided with above the smooth transmission layer, it is described scalable flexible saturating There is space to avoid the scalable flexible and transparent protective layer from being passed through with the light between bright protective layer and the smooth transmission layer Layer is in contact；The edge of the scalable flexible and transparent protective layer is connected with insulating supporting structure, the bottom of insulating supporting structure Around the edge for being arranged at the corresponding smooth transmission layer, so as to support scalable flexible and transparent protective layer；It is described scalable soft Property protective clear layer realize masking or exposure to the smooth transmission layer by stretching or crimping.

Preferably, the state of curling includes a-circle-by-a-circle rolling from inside to outside and forms a volume.

Preferably, the scalable flexible and transparent protective layer has two-layer, and ground floor is hydrophily hyaline layer, in light Light transmission layer is protected during according to intensity less than set intensity of illumination threshold value, so as to reduce scalable flexible and transparent protective layer and light Organic pollution in transmission layer；The second layer is hydrophobic transparent layer, for exceeding set humidity threshold in ambient humidity When protect light transmission layer so that suppress moisture into the smooth transmission layer and enter solar film battery in；Hydrophily is transparent Another insulating supporting structure is connected between the edge of layer and hydrophobic transparent layer, for isolating and supporting two-layer hyaline layer.

Preferably, described insulating supporting structure includes upper insulating supporting structure and lower insulating supporting structure；It is described exhausted Edge supporting construction is located at the top of the lower insulating supporting structure, and the width of the upper insulating supporting structure is lower exhausted less than described The width of edge supporting construction so that the part that lower insulating supporting structure is located on the inside of upper insulating supporting structure is exposed and is used for One layer scalable flexible and transparent protective layer of the support on lower insulating supporting structure；The top of upper insulating supporting structure is used for branch One layer scalable flexible and transparent protective layer of the support on upper insulating supporting structure.

Preferably, also with controller, the first converter, the second converter and determining device, controller is mutually electric with determining device Even, determining device is mutually electrically connected with converter；The graphene-based laminated film of light transmission layer includes：Optical detection region, shines for detecting It is mapped to intensity of illumination on solar cell；And humidity search coverage, for detecting the humidity around solar cell；

Optical detection region is mutually electrically connected with the first converter, for detecting the intensity of illumination of surrounding environment and producing electric signal to send out The first converter is given, the electric signal is converted to intensity of illumination data is activation to determining device by the first converter, and determining device judges Whether the intensity of illumination data are higher than set intensity of illumination threshold value；If it has, then determining device sends contraction signal to control Device, the controller control scalable flexible and transparent protective layer performs crimping action；If it has not, then determining device sends stretch signal To controller, the controller control scalable flexible and transparent protective layer performs stretching；

Humidity search coverage is mutually electrically connected with the second converter, for detecting the humidity of surrounding environment and producing electric signal to send To the second converter, the electric signal is converted to humidity data and is sent to determining device by the second converter, and determining device judges the humidity Whether data are higher than set humidity threshold；If it has not, then determining device sends contraction signal to controller, controller control institute State scalable flexible and transparent protective layer and perform crimping action；If it has, then determining device sends stretch signal to controller, controller The scalable flexible and transparent protective layer is controlled to perform stretching.

Preferably, in the range of set intensity of illumination, the humidity threshold is set for the intensity of illumination threshold value Humidity range in.

Preferably, the hydrophily hyaline layer and hydrophobic transparent layer default conditions are rolled state.

Preferably, the hydrophily hyaline layer is the graphene film of individual layer atomic layer.

Preferably, the hydrophobic transparent layer is two-layer or three layers of graphene film of atomic layer.

Preferably, the light conversion layer is dye-sensitized layer, also has bottom electrode layer in light conversion layer bottom.

Graphene-based laminated film of the present utility model and solar film battery, vertical-growth goes out on graphene film Continuous Nanometer Thin Films by Sol-Gel Method, during using the laminated film as light transmission layer, the high transmittance of graphene film ensure that this is answered Film is closed as the light transmission rate higher of light transmission layer, self-cleaning function is realized using Nanometer Thin Films by Sol-Gel Method；Further , using the graphene-based laminated film as electrode layer, improved using the quick carrier mobility of graphene film and led Electric speed, reduces loss of the battery in opto-electronic conversion, by the use of the nano thin-film perpendicular to graphene film as dye migration Passage, improves dye migration speed, and then improve generating efficiency.

Brief description of the drawings

Fig. 1 a are the cross section structure schematic diagram of the solar film battery of embodiment of the present utility model

Fig. 1 b are the overlooking the structure diagram of the rounded solar film battery of embodiment of the present utility model

Fig. 1 c are the overlooking the structure diagram of the solar film battery being rectangle of embodiment of the present utility model

Fig. 2 is the scalable flexible and transparent protective layer of embodiment of the present utility model in schematic diagram when crimping

Fig. 3 is each structural relation schematic diagram of the solar cell of embodiment of the present utility model

Fig. 4 is the hydrophilic transparent layer and state of the hydrophobic hyaline layer on daytime and fine day of embodiment of the present utility model Schematic diagram

Fig. 5 is the hydrophilic transparent layer and state of the hydrophobic hyaline layer on daytime and rainy day of embodiment of the present utility model Schematic diagram

Fig. 6 is the hydrophilic transparent layer and state of the hydrophobic hyaline layer at night and fine day of embodiment of the present utility model Schematic diagram

Fig. 7 is the hydrophilic transparent layer and state of the hydrophobic hyaline layer at night and rainy day of embodiment of the present utility model Schematic diagram

Fig. 8 is the overlooking the structure diagram of the graphene-based laminated film of embodiment of the present utility model

Fig. 9 is the cross section structure schematic diagram of the graphene-based laminated film of embodiment of the present utility model

Figure 10 is the preparation method of the graphene-based automatically cleaning solar film battery of embodiment of the present utility model two Schematic flow sheet

Figure 11-15 is the preparation method of the graphene-based automatically cleaning solar film battery of embodiment of the present utility model two Each preparation process schematic diagram

Figure 16-19 is the upper insulating supporting structure of embodiment of the present utility model two and the preparation system of lower insulating supporting structure Each step schematic diagram of standby process

Figure 20 is the schematic flow sheet of the preparation method of the graphene-based laminated film of embodiment of the present utility model two

Figure 21-23 illustrates for each step of the preparation method of the graphene-based laminated film of embodiment of the present utility model two Figure

Figure 24-26 is each step schematic diagram of the nano thin-film growth course of embodiment of the present utility model two

Figure 27-28 is each step schematic diagram of the preparation process of the one-dimensional nano line array of embodiment of the present utility model two

Figure 29-31 is each step schematic diagram of the preparation process of the one-dimensional nano line array of embodiment of the present utility model two

Specific embodiment

To make content of the present utility model more clear understandable, below in conjunction with Figure of description, to of the present utility model interior Appearance is described further.Certain the utility model is not limited to the specific embodiment, known to those skilled in the art General replacement be also covered by protection domain of the present utility model.

Embodiment one

The utility model is described in further detail below in conjunction with accompanying drawing 1-9 and specific embodiment.It should be noted that, it is attached Figure using very simplify in the form of, using non-accurately ratio, and be only used to conveniently, clearly reach aid in illustrating this implementation The purpose of example.

Fig. 1 a are referred to, the graphene-based automatically cleaning solar film battery of the present embodiment, is thin dye sensitization of solar Film battery, it includes：Light transmission layer G03, transparent electrode layer G02 and light conversion layer G01 are disposed with from top to bottom, this In, also there is bottom electrode layer G04 in light conversion layer G01 bottoms；Incident light is successively through light transmission layer G03 and transparent electrode layer G02, enters back into light conversion layer G01, and light conversion layer G01 carries out opto-electronic conversion and produce electricity after absorbing incident light；Light is passed through Layer G03 is graphene-based laminated film, as shown in Figure 1a, the graphene-based laminated film bag of the light transmission layer G03 of the present embodiment Include：Graphene film D031；Vertical-growth is in the nano thin-film D032 (shown in dotted line frame) on graphene film D031；This reality Applying has multiple row nano thin-film D032 in example on graphene film D031.The plane of nano thin-film D032 and graphene film D031 Vertically.Please continue to refer to Fig. 1 a, the bottom of graphene film D031 is located at transparent electrode layer G02 upper surfaces.Light conversion layer G01 can Think dye-sensitized layer, automatically cleaning solar film battery also has another electrode layer, for dyestuff two electrode layers it Between conversion and migration provide passage, arrow show dye migration direction in such as Fig. 1 a, so as to improve photoelectric transformation efficiency.This In use graphene-based laminated film, make use of its light transmission rate high and the photocatalytic semiconductor material can be with catalyzing organic To realize the self-cleaning function of solar cell.Also, in light transmission layer G03, nano thin-film D032 is perpendicular to graphene film D031 grows, and there is also certain spacing between multiple nano thin-film D032, can also be by setting multiple nano thin-films Photocatalysis efficiency and light transmission rate that spacing between D032 is optimal in an OK range, for example, light transmission layer G03 In graphene film D031 on there is multiple nano thin-film D032 being arranged in array, and the nanometer in light transmission layer G03 Spacing between film D032 is more than 10nm, so as to will not be covered on graphene film as traditional nano thin-film (mutually flat OK) cause the light transmission rate of graphene film to substantially reduce problem to occur, thus, do not interfere with the entirety of solar cell Light transmission rate and light conversion efficiency.Preferably, nano thin-film D032 has multiple micro- engraved structures, so as to constitute nano net, come It is effective to improve photocatalysis efficiency and automatical cleaning ability.

In the present embodiment, transparent electrode layer G02 is also adopted by graphene-based laminated film；Specifically, light transmission layer G03's The contact of graphene film D031 lower surfaces is provided with transparent substrate D023, and the graphene film D021 of transparent electrode layer G02 is tight Patch transparent substrate D023 lower surfaces, the nano thin-film D022 in the graphene-based laminated film of transparent electrode layer G02 is located at it The lower surface of graphene film D021.Here, transparent electrode layer G02 uses graphene-based laminated film, using graphene film Outstanding electric conductivity improve conductance reduce loss, and insert perpendicular to the nano thin-film D022 of graphene film D021 Passage can be provided for the migration of dyestuff in light conversion layer G01, improve mobility and conversion efficiency, further, nano thin-film D022 has multiple micro- engraved structures, so as to constitute nano net to improve the capture ability to dyestuff, further improves the effect that generates electricity Rate.Here, in transparent electrode layer G02, the density of nano thin-film D022 should also be as considering the problem of light transmission rate, nano thin-film It is slightly larger that spacing between D022 can be set, preferably, between nano thin-film D022 in transparent electrode layer G02 Spacing is more than 10nm.

In the present embodiment, please continue to refer to Fig. 1 a, scalable flexible and transparent protection is additionally provided with above light transmission layer G03 Layer C1, C2, it is scalable flexible saturating to avoid to have space between scalable flexible and transparent protective layer C1, C2 and light transmission layer G03 Bright protective layer C1, C2 are in contact with light transmission layer G03；The edge of scalable flexible and transparent protective layer C1 is connected with lower insulating supporting The material of structure Z1, lower insulating supporting structure Z1 here is insulating materials, and the bottom part ring of lower insulating supporting structure Z1 is around setting In the edge of corresponding light transmission layer G03, so as to support scalable flexible and transparent protective layer C1；Scalable flexible and transparent protective layer C1, C2 realize masking or exposure to light transmission layer G03 by stretching or crimping.Here curling can be including from inside to outside one That encloses rolls and forms a volume, as shown in Figure 2.When extended, the state from volume is flexed outward in plane.On volume The active force that the execution of bent or stretching need to be used includes the extraneous electric field force or electrostatic force given, for example, default conditions are in Curling, makes scalable flexible and transparent protective layer C1, C2 have the normality of curling using memory technique such as stress memory, works as needs When scalable flexible and transparent protective layer C1, C2 stretch, electric field can be applied to scalable flexible and transparent protective layer C1, C2, making can Telescopic flexible protective clear layer C1, C2 surfaces produce identical charges, due to curling so that scalable flexible and transparent protective layer C1, C2 has the adjacently situated surfaces of curling, mutually exclusive between the adjacently situated surfaces of curling according to principle of same-sex repulsion so that scalable soft Property protective clear layer C1, C2 are gradually extended.

Specifically, please continue to refer to Fig. 1 a, scalable flexible and transparent protective layer C1, C2 have two-layer, ground floor is hydrophilic Property hyaline layer C1, for protecting light transmission layer when intensity of illumination is less than set intensity of illumination threshold value, so as to reduce itself Organic pollution and light transmission layer G03 organic pollution；The second layer is hydrophobic transparent layer C2, in ambient humidity Light transmission layer G03 is protected during more than set humidity threshold, so as to suppress moisture into light transmission layer G03 and enter solar energy In hull cell.It should be noted that in the vertical direction of the utility model to hydrophilic transparent layer C1 and hydrophobic hyaline layer C2 Order be not restricted, for example, hydrophilic transparent layer C1 may be located on hydrophobic hyaline layer C2, it is also possible to positioned at hydrophobic hyaline layer Under C2.Here, intensity of illumination threshold value can be in the range of set intensity of illumination, and humidity threshold can be set wet In the range of degree.

In the present embodiment, insulating supporting structure Z2, upper insulating supporting structure are additionally provided with lower insulating supporting structure Z1 Z2 and lower insulating supporting structure Z1 can be integrally formed, or be molded twice, and the width of upper insulating supporting structure Z2 is small In the width of lower insulating supporting structure Z1 so that the part that lower insulating supporting structure Z1 is located on the inside of upper insulating supporting structure Z2 is sudden and violent The hydrophilic transparent layer C1 for exposing and being used to support on lower insulating supporting structure Z1；Use at the top of upper insulating supporting structure Z2 In hydrophobic hyaline layer C2 of the support on upper insulating supporting structure Z2, so that two-layer hyaline layer C1, C2 are located at down respectively On insulating supporting structure Z1 and upper insulating supporting structure Z2, the top of upper insulating supporting structure Z2 and lower insulating supporting structure Z1's Top has certain spacing, for isolating two-layer protective clear layer C1, C2, and leaves the transparent of enough space empty lower floors Protective layer C1 is crimped or stretches；Upper insulating supporting structure Z2 and lower insulating supporting structure Z1 is around the side of light transmission layer G03 Edge is set.In the present embodiment, hydrophilic transparent layer C1 can be the graphene film of individual layer atomic layer, and hydrophobic hyaline layer C2 can be Two-layer or three layers of graphene film of atomic layer.In the present embodiment, the width of lower insulating supporting structure Z1 is more than upper insulating supporting The width of structure Z2 so that the hydrophilic transparent of hydrophobic hyaline layer C2 and lower insulating supporting structure Z1 on upper insulating supporting structure Z2 Layer C1 is not interfered with each other when performing curling or stretching respectively.

In the present embodiment, when solar film battery is for circle, incorporated by reference to Fig. 1 a and Fig. 1 b, upper insulating supporting structure Z2 Become narrow gradually to B sides from A sides, but it is highly constant；Lower insulating supporting structure Z1 is constant from A sides to B sides width or gradually broadens, But it is highly constant；Certainly, the height of upper insulating supporting structure Z2 can also gradually uprise or become short, lower insulating supporting structure Z1 Height can also gradually uprise or become short, upper insulating supporting structure Z2 and lower insulating supporting structure Z1 is gradually uprised or gradually The trend for becoming short can be with consistent or opposite；So, protective clear layer C1, C2 can not only can be obtained in curling or stretching, extension To powerful support, can also save shared because of this gradual change width of upper insulating supporting structure Z2 and lower insulating supporting structure Z1 Light transmission layer G03 superjacent air spaces, and upper insulating supporting structure Z2 and lower insulating supporting structure Z1 gradual changes width cooperate, So that the hydrophilic transparent layer C1 difference of the hydrophobic hyaline layer C2 and lower insulating supporting structure Z1 on upper insulating supporting structure Z2 Do not interfered with each other when performing curling or stretching.Meanwhile, one end of the hydrophobic hyaline layer C2 on upper insulating supporting structure Z2 is consolidated Surely insulating supporting structure Z1 regions most wide (A sides dotted line frame) are bonded to, the hydrophilic transparent layer on lower insulating supporting structure Z1 One end retainingf key of C1 is together in region (B sides dotted line frame) lower insulating supporting structure Z1 most wide.Preferably, the solar energy of circle is thin Film battery fixes one end A sides dotted line frame and lower insulating supporting structure Z1 of the hydrophobic hyaline layer C2 of bonding in upper insulating supporting structure Z2 One end of fixed bonding hydrophilic transparent layer C1 (B sides dotted line frame) is set to straight line plane rather than arc surface, dotted line frame in such as Fig. 1 b Shown, dotted line frame also may indicate that the position of fixed bonding sets the plane that is in line.

In the present embodiment, when solar film battery is rectangle, upper insulating supporting structure Z2 and lower insulation accordingly It is rectangle that supporting construction Z1 overlooks figure, and incorporated by reference to Fig. 1 a and Fig. 1 c, upper insulating supporting structure Z2 gradually becomes from C sides to D sides It is narrow but highly constant；Lower insulating supporting structure Z1 is constant from C sides to D sides width or gradually broadens, but highly constant；Certainly, on The height of insulating supporting structure Z2 can also gradually uprise or become short, and the height of lower insulating supporting structure Z1 can also be gradually Uprise or become short, upper insulating supporting structure Z2 and lower insulating supporting structure Z1 is gradually uprised or gradually become short trend can phase one Cause or opposite；Meanwhile, one end retainingf key of the hydrophobic hyaline layer C2 on upper insulating supporting structure Z2 is together in upper insulating supporting structure Side (shown in the dotted line frame of C sides) Z2 most wide, on lower insulating supporting structure Z1 hydrophilic transparent layer C1 one end retainingf key together in Side lower insulating supporting structure Z1 most wide (shown in the dotted line frame of D sides).

Also, it should be noted that the overall structure of solar film battery of the present utility model can also be square, ellipse The other structures such as circle.

Fig. 3 is referred to, the graphene-based automatically cleaning solar film battery of the present embodiment also has controller, the first conversion Device, the second converter and determining device, controller are mutually electrically connected with determining device, and determining device is mutually electrically connected with converter；The stone of light transmission layer Mertenyl laminated film includes：Optical detection region, intensity of illumination on solar cell is irradiated to for detecting；And humidity detection Region, for detecting the humidity around solar cell；

Optical detection region is mutually electrically connected with the first converter, for detecting the intensity of illumination of surrounding environment and producing electric signal to send out The first converter is given, the electric signal is converted to intensity of illumination data is activation to determining device by the first converter, and determining device judges Whether the intensity of illumination data are higher than set intensity of illumination threshold value；If it has, then determining device sends contraction signal to control Device, controller controls the hydrophilic transparent layer of scalable flexible and transparent protective layer to perform crimping action；If it has not, then determining device sends To controller, controller controls the hydrophilic transparent layer of the scalable flexible and transparent protective layer to perform stretching to stretch signal；

Humidity search coverage is mutually electrically connected with the second converter, for detecting the humidity of surrounding environment and producing electric signal to send To the second converter, the electric signal is converted to humidity data and is sent to determining device by the second converter, and determining device judges the humidity Whether data are higher than set humidity threshold；If it has not, then determining device sends contraction signal to controller, controller control institute The hydrophobic hyaline layer for stating scalable flexible and transparent protective layer performs crimping action；If it has, then determining device send stretch signal to Controller, controller controls the hydrophobic hyaline layer of the scalable flexible and transparent protective layer to perform stretching.

Additionally, in whole graphene-based automatically cleaning solar film battery, light transmission layer G03, transparent electrode layer G02 are adopted It is exactly with another clear superiority of graphene film：Due to the good thermal conductivity of graphene film, can radiate in time, it is to avoid Because heat effect produces expansion or shrinkage to cause the problem of deformation between the structure at all levels of automatically cleaning solar film battery, So as to improve the service life of solar cell and keep good performance for a long time.Meanwhile, it is graphene-based when the present embodiment Automatically cleaning solar film battery can be applied to the occasion of printing opacity, for example, being applied on window, being applied to computer or hand Machine screen is first-class, naturally it is also possible to be applied to not need the occasion of printing opacity.When light conversion layer is also adopted by flexible material, this implementation The graphene-based automatically cleaning solar film battery of example is possible to realize bending adapt to the occasion with given shape so that this The solar film battery application of embodiment is more flexible.

In the present embodiment, hydrophily hyaline layer C2 and hydrophobic transparent layer C1 default conditions are rolled state；Intensity of illumination The illumination on daytime and the illumination at night that the setting of threshold value can be experienced for 24 hours according to one day count a suitable model Enclose, here, daytime is that when having solar irradiation, solar cell can be to collect sunshine, now, light transmission is not blocked Layer；Night is when not having sunlight, solar cell can not mobile phone sunshine, now, if exposure light for a long time Transmission layer can be polluted, and can be extended using hydrophilic transparent layer, light transmission layer be sheltered from, so as to reduce light transmission layer Pollution, and because using hydrophilic transparent layer, organic pollution is not easy to be attached to hydrophilic transparent layer surface, further drop The pollution of low hydrophilic transparent layer；The setting of humidity threshold should be solar cell receptible humidity greatest limit, But for safer consideration, humidity threshold can be set extremely low, when rainy, the humidity for now being detected is much Beyond humidity threshold, therefore, it is necessary to be covered up light transmission layer using hydrophobic hyaline layer when rainy；When fine day, will dredge Water hyaline layer is accepted, and light transmission layer is not blocked, it is to avoid influence the transmission of sunshine at many levels excessively.It should be noted that this In intensity of illumination except that using in addition to sunshine, light, such as fluorescent lamp etc. can also be utilized to realize opto-electronic conversion.

Below refering to Fig. 4~7 come describe hydrophilic transparent layer and hydrophobic hyaline layer stretching, extension or rolled state with environment change Change, and following be described so that hydrophilic transparent layer is located at hydrophobic hyaline layer lower section as an example.

Refer to Fig. 4, Fig. 4 is the hydrophilic transparent layer and hydrophobic hyaline layer of embodiment of the present utility model on daytime and fine It when view, now, hydrophilic transparent layer C1 and hydrophobic hyaline layer C2 into rolled state so that solar energy Enough it is directly incident on light transmission layer G03, it is to avoid the consumption of sunshine；

Fig. 5 is referred to, Fig. 5 is the hydrophilic transparent layer and hydrophobic hyaline layer of embodiment of the present utility model in daytime and rain It when view, now, hydrophilic transparent layer C1 be in rolled state, hydrophobic hyaline layer C2 be in extended configuration so that Moisture can not enter light transmission layer G03, realize protection to light transmission layer G03, also, only be blocked with layer of transparent layer C2, The consumption to sunshine can be reduced relative to two-layer hyaline layer C1, C2, although rainy day sunshine is weaker, but still can be with profit With.

Refer to Fig. 6, Fig. 6 is the hydrophilic transparent layer and hydrophobic hyaline layer of embodiment of the present utility model at night and fine It when view, now, hydrophilic transparent layer C1 be in extended configuration, hydrophobic hyaline layer C2 be in rolled state, hydrophilic transparent Layer C1 blocks light transmission layer so that solar cell carries out automatically cleaning protection when not working to light transmission layer G03.

Fig. 7 is referred to, Fig. 7 is the hydrophilic transparent layer and hydrophobic hyaline layer of embodiment of the present utility model in night and rain It when view, now, hydrophilic transparent layer C1 be in extended configuration, hydrophobic hyaline layer C2 be in extended configuration, it is hydrophobic transparent Layer C2 can exclude rainwater into light transmission layer G03, and hydrophilic transparent layer C1 can also further carry out automatically cleaning protection.

It should be noted that in the present embodiment hydrophilic transparent layer C1, hydrophobic hyaline layer C2 with daytime, night, fine day Various states with the rainy day are example, and the setting of other rational states is still within protection domain of the present utility model；Meanwhile, Utilization of the solar cell of the present utility model to light is not limited to sunshine, can also utilize the luminous energy of other forms, certainly, matches somebody with somebody Various application and environments are closed, hydrophilic transparent layer, hydrophobic hyaline layer can show different mated conditions, and various conversion are at this Within the thought of utility model.

Next, in the graphene-based automatically cleaning solar film battery of specific descriptions the present embodiment in light transmission layer G03 And transparent electrode layer G02 graphene-based laminated film structure, it is in light transmission layer G03 and saturating in the present embodiment The structure of the graphene-based laminated film of prescribed electrode layer G02 is identical.Fig. 8 and Fig. 9 is referred to, the graphene-based of the present embodiment is combined Film includes：One graphene film 101；Vertical-growth is in the nano thin-film (shown in dotted line frame) on graphene film 101；This Illustrate only two row nano-wire arrays on graphene film 101 in the accompanying drawing 8 and 9 of embodiment, then the graphite of the present embodiment There is multiple row nano-wire array, accompanying drawing 8 and 9 is only intended to explanation, but this is not used in and limits of the present utility model on alkene film 101 Protection domain.The plane of nano thin-film (shown in dotted line frame) is vertical with transparent substrates 101；Nano thin-film has multiple micro- hollow outs Structure 103, so that nano net is formed, and the bottom of nano thin-film is mutually bonded with graphene film 101 by chemical bond；Nanometer thin The material of film is conductor photocatalysis material.In the present embodiment, micro- engraved structure 103 is micro- to engrave in the array arrangement being alternately staggered Hollow structure 103 may be located at the side wall touching position of the nano wire 102 for constituting nano thin-film, it is also possible on nano wire 102. Here nano thin-film is to be grown perpendicular to graphene film 101 by nano wire 102 and the side of adjacent nanowires 102 is in contact Nano thin-film is formed, further can etch to form micro- void region 103 through nano thin-film.Meanwhile, the nano wire being in contact Mutually it is bonded by chemical bond between 102, can be caused adjacent due to being in contact during the lateral growth of adjacent nanowires 102 The a certain degree of continued growth in the interface of nano wire 102, so that due to there is these chemistry between these nano wires 102 for being in contact The combination of key and more firmly, so as to constitute a nano thin-film.Here, the diameter of nano wire 102 is the thickness of nano thin-film Degree, can by controlling growth technique such as time, temperature etc. to control adjacent nanowires 102 to be in contact when diameter so that The nano thin-film of thickness needed for being formed；The height of nano thin-film can also be controlled by controlling growth technique simultaneously, so that To relatively thin and shorter nano thin-film, to improve the specific surface area and photocatalytic activity of nano thin-film, while can also avoid receiving Rice film is blocked up or the too high transparency for reducing whole graphene-based laminated film.Preferably, the thickness of nano thin-film is little In 10nm, for example, 5-7nm.Preferably, the graphene film 101 of the present embodiment is single-layer graphene film.

In the present embodiment, because nano thin-film needs that with photocatalysis performance photo-catalysis capability can be realized, therefore, receive The material of rice film is conductor photocatalysis material.Preferably, catalysis material is broad-band gap catalysis material.Accordingly, receive Rice noodles 102 can also be wide band gap semiconducter nano wire, for example, titanium alloy nano line or zinc alloy nano-wire, and, both The cost of alloy material is relatively low, advantageously in large-scale production.Wherein, titanium alloy nano line can select to be titanium dioxide Nano wire, zinc alloy nano-wire can select to be zinc oxide nanowire；The crystal formation of titanium dioxide nano thread can be Ca-Ti ore type Or rutile-type, the crystal formation of zinc oxide nanowire is hexahedron structure.

It should be noted that when nanowire sidewalls are in contact, merged between nanowire sidewalls, if for example, nano wire It is titanic oxide material, then is merged between adjacent nano line side wall.

In the present embodiment, micro- engraved structure 103 can be nanometer level microporous, preferably, nanometer level microporous can be not more than 10nm, it is preferable that no more than 5nm；Preferably, the spacing between adjacent micro- engraved structure 103 is not more than 10nm.Micro- hollow out knot The setting of structure 103, not only increases the specific surface area of nano net, also improves the adsorption efficiency of nano net, meanwhile, micro- hollow out knot The nano net that structure 103 is formed from for another angle, equivalent to being that multiple smaller nanostructureds are constituted in nano net, So as to further increase the photocatalysis effect of nano net.It should be noted that micro- engraved structure of the present utility model is not limited to The present embodiment it is nanometer level microporous, shape is not limited to circle, can also be other shapes, such as：Regular polygon, irregular figure Deng the utility model is not restricted to this.

Further, in order to not influence the light transmission rate of whole graphene-based laminated film, multiple nano thin-films are in array Arrangement, and spacing between adjacent nano film should be slightly larger, preferably, the spacing between adjacent nano film is more than 10nm。

Additionally, nano net can be also used for filtering, detection of gas.When micro- engraved structure 103 is for nanometer level microporous, particularly When spacing between adjacent micro- engraved structure 103 is not more than 10nm, the filtering of bigger molecule is can be also used for.

Embodiment two

The utility model is described in further detail below in conjunction with accompanying drawing 10-27 and specific embodiment.It should be noted that, Accompanying drawing using very simplify in the form of, using non-accurately ratio, and be only used to conveniently, clearly reach aid illustration this reality Apply the purpose of example.

Figure 10 is referred to, in the present embodiment two, to the graphene-based automatically cleaning solar film battery of above-described embodiment one Preparation method, including：

Step 0001：Figure 11 is referred to, a light conversion layer G01 is prepared；

Specifically, step 0001 is specifically included：One substrate SUB is provided；On substrate SUB prepare bottom electrode layer G04 and Light conversion layer G01；Light conversion layer G01 can change organic layer for dye sensitization light.

Step 0002：Figure 12 is referred to, transparent electrode layer G02 is formed on light conversion layer G01；

Step 0003：Figure 13 is referred to, light transmission layer G03 is formed on transparent electrode layer G02.

In the present embodiment, step 0004 is also included after step 0003：Figure 14 is referred to, on the side of light transmission layer G03 Edge region forms insulating supporting structure Z1, Z2；Then, it is the edge bottom of scalable flexible and transparent protective layer C1, C2 is corresponding Be bonded in insulating supporting structure Z1, Z2 surfaces so that the edge of scalable flexible and transparent protective layer C1, C2 is connected to On insulating supporting structure Z1, Z2.Here insulating supporting structure Z1, Z2 can be insulating barrier, scalable flexible and transparent protective layer C1, C2 can be graphene film.

It should be noted that here, upper insulating supporting structure Z2 and lower insulating supporting structure on above-described embodiment one The preparation of Z1 can include：First, depositing insulating layer, then use but be not limited to photoetching and etching technics come etch it is upper insulation branch The pattern of support structure Z2 and lower insulating supporting structure Z1, for example, the upper insulating supporting structure Z2 of certain depth can be etched first Pattern, then the pattern for etching lower insulating supporting structure Z1；Or：The first layer insulating is first deposited, is then used but is not limited The pattern of lower insulating supporting structure Z1 is etched in the first layer insulating in photoetching and etching technics；Photoresist is coated with, and Form the area of the pattern of upper insulating supporting structure Z2 in the photoresist through photoetching, then deposit the second layer insulating in photoresist In the area of the pattern of upper insulating supporting structure Z2, remaining photoresist is then removed, so as to obtain upper insulating supporting structure Z2.This Outward, it is contemplated that deposition and damage of the etching technics to light transmission layer G03, can use and be bonded in insulating supporting structure Z1, Z2 The technique of light transmission layer G03 fringe regions, it is specifically included：First, Figure 16 is referred to, the depositing insulating layer on a substrate J01 J02, then, refer to Figure 17, through photoetching and etching so as to prepare insulating supporting structure Z2 on inverted in insulating barrier J02 With lower insulating supporting structure Z1；Refer to Figure 18 again, substrate J01 be inverted, so as to by upper insulating supporting structure Z2 and Lower insulating supporting structure Z1 is inverted；And bonding technology is used, makes the bottom of lower insulating supporting structure Z1 and light transmission layer The fringe region of G03 is mutually bonded；Finally, Figure 19 is referred to, substrate J01 is peeled off, for example, substrate J01 is had using readily soluble Machine material, can be eroded substrate J01 using corresponding liquid；Or, substrate SUB is made with upper insulation branch using chemical liquid The interface peel that support structure Z2 is in contact.If the substrate SUB materials employed in substrate J01 adopted here and step 0001 Material is identical, can be eroded using identical liquid or using being bonded of the destruction of identical liquid substrate SUB and bottom electrode layer G04, And destruction substrate J01 and upper insulating supporting structure Z2 are bonded, so as to the two be peeled off together.

Also include step 0005 afterwards：Figure 15 is referred to, the structure for completing step 0004 is separated with substrate SUB. The detailed description of the graphene-based automatically cleaning solar cell on the present embodiment two may refer to embodiment one, no longer go to live in the household of one's in-laws on getting married here State.

Next, the method for the graphene-based laminated film to preparing embodiment one is described in further details.

Figure 20 is referred to, is illustrated by taking two row nano-wire arrays on graphene film as an example in the present embodiment two, but this It is not used in limitation protection domain of the present utility model.In the present embodiment, the system of the graphene-based laminated film of above-described embodiment one Preparation Method includes：

Step 01：Refer to Figure 21, there is provided a graphene film 101；Here, preferably, the graphene film is individual layer Graphene film, the preparation on single-layer graphene film can be prepared using chemical meteorology deposition method, high-temperature decomposition etc., This is that those skilled in the art could be aware that, is repeated no more here.

Step 02：Figure 22 is referred to, nano thin-film (shown in dotted line frame) is grown on graphene film 101；Grown Nano thin-film where plane perpendicular to graphene film 101, bottom and the graphene film 101 of nano thin-film pass through chemical bond Mutually it is bonded；Chemical bond is between the atom and the atom of the material composition of graphene film 101 in nano film material composition Bonding, for example, the material of nano thin-film be titanium dioxide, then the titanium atom of titanium dioxide and/or or oxygen atom it is thin with Graphene The carbon atom of film 101 is mutually bonded and obtains Ti-C keys and/or C-O keys.

In the present embodiment, after step 02, can also include：

Step 03：Figure 23 is referred to, multiple micro- engraved structures 103 are etched on nano thin-film (shown in dotted line frame). Here it is possible to using plasma lithographic technique or laser-induced thermal etching etch micro- engraved structure 103.

Specifically, in the present embodiment, nano thin-film in illustrating step 02 by taking one layer of growth of nano thin-film as an example below Growth course, it includes：

Step 021, refers to Figure 24, and 1-dimention nano sub-array 201 is prepared on graphene film 101；For example, metatitanic acid Seed solution or zinc acetate seed solution, this is that those skilled in the art could be aware that, is repeated no more here.

Step 022, refers to Figure 25, and with nanometer sub-array 201 as base, every nanometer seed is bent to growth nanowire 202, so as to form nano-wire array；Here it is possible to using chemical vapour deposition technique, aqua-solution method or electrochemical plating next life Nano wire long 202.For example, preparing titanium dioxide nano thread using hydro-thermal method, solution concentration is placed in for 0.04M precursor solutions In reactor, at a temperature of 100~150 DEG C, constant temperature grows 01~0.5 hour, finally can obtain diameter less than the two of 10nm Titanium oxide nano wire.Again for example, preparing zinc oxide nanowire using hydro-thermal method, solution concentration is put for 0.05M precursor solutions In reactor, at a temperature of 90~140 DEG C, constant temperature grows 01~0.5 hour, finally can obtain oxygen of the diameter less than 10nm Change zinc nano wire.Preparation on nano wire is also the ordinary skill in the art, is that those skilled in the art could be aware that, this In repeat no more.

Step 023, refers to Figure 26, and the side of adjacent nanowires contacts with each other, so as to be formed perpendicular to graphene film Nano thin-film.The diameter of the nano wire 203 in step 023 is all higher than the diameter of the nano wire 202 in step 022, step 023 In the length of nano wire 203 be all higher than the length of the nano wire 202 in step 022, for example, being further continued for above-mentioned growth conditions not Become, extension growth time 0.1~0.5 hour so that nano wire cross growth is contacted, so as to form required nano titania Film or zinc oxide nano film.The growth technique of nano wire can use conventional method, for example, can be by other conditions not Become, extend growth time, or the longitudinal growth that nano wire is realized by the different growth temperature of two steps or precursor concentration And cross growth.

Here, the controllable of nanowire diameter can take following manner when realizing that nanowire sidewalls contact with each other：

It is possible, firstly, to by it is substantial amounts of experiment obtain other conditions it is constant when, under precursor solution concentration permanence condition Nano wire longitudinal direction average growth rate and horizontal average growth rate；And when other conditions are constant, it is dense in precursor solution Degree is different such as nano wire longitudinal direction average growth rate under conditions of concentration M1 or M2 and horizontal average growth rate；Similarly, also may be used To obtain the nano wire longitudinal direction average growth rate and horizontal average growth rate under the conditions of different temperatures P1 or P2.

Then, according to the average growth rate tried to achieve, under the conditions of corresponding growing environment, the target of nano wire is set Diameter D and target length L；

Then, according to aimed dia D, the position of nano wire is set on a transparent substrate, the position of nano wire that is to say kind The position of son；The theoretical spacing of seed is also D, in actual process, it may appear that multiple seeds assemble situation, as long as in the model of D There is at least one seed, so, if it is to be capable of achieving to form one-dimensional continuous nanometer seed membrane in enclosing；Furthermore, it is also possible to It is combined using template and etching technics, the preparation of specific 1-dimention nano sub-array will be in subsequent detailed description.

Then, the calculating of growth time and diameter on step 22 and step 23 can use following process：

A kind of method is：The average longitudinal growth speed of D/ is obtained required time t1 by setting, and L/ average transverses are grown into speed Rate obtain the time required to t2, it is contemplated that required nanowire diameter is the principal element for determining nanometer thickness of net, no matter t1 and t2 How is size, and selected actual growth time t should be greater than or equal to time t1；In the premise that nanowire growth environment is constant Under, substantial step 022 and step 023 are a continuous processes, and the total growth time that need to only set nano wire is t.

Another method is：Can be received according under conditions of precursor solution concentration difference when other conditions are constant Rice noodles longitudinal direction average growth rate and horizontal average growth rate, using the aimed dia D and target length L that set nano wire, The precursor concentration for step 022 and step 023 is selected respectively, and calculates corresponding growth time, now, step 022 The concentration of precursor solution is set to M1, and growth time is set to T1；The concentration of the precursor solution of step 023 is set to M2, then basis Nano wire longitudinal direction average growth rate V1 (being obtained by many experiments before) under concentration M1, obtains step 022 complete Into the diameter D1=V1*T1 of rear nano wire；Again by aimed dia D-D1, difference in diameter D2 is obtained, then, according under concentration M2 Nano wire longitudinal direction average growth rate V2 (being obtained by many experiments before), during growth needed for obtaining step 023 Between T2=D2/V2.In this case, preferably, selected precursor solution concentration M1 ＜ M2 so that the transverse direction of step 023 is raw Shorten for a long time.

Yet another method is：Can be indulged according to the nano wire under conditions of growth temperature difference when other conditions are constant To average growth rate and horizontal average growth rate, using the aimed dia D and target length L that set nano wire, select respectively The precursor concentration for step 022 and step 023 is selected, and calculates corresponding growth time, now, the growth temperature of step 022 Degree is set to P1, and growth time is set to T1；The growth temperature of step 023 is set to P2, then according to the nano wire under growth temperature P1 Longitudinal average growth rate V1 (being obtained by many experiments before), obtains the diameter D1 of nano wire after the completion of step 022 =V1*T1；Again by aimed dia D-D1, difference in diameter D2 is obtained, it is then, longitudinally flat according to the nano wire under growth temperature P2 Equal growth rate V2 (being obtained by many experiments before), the growth time T2=D2/V2 needed for obtaining step 023.Should In the case of, preferably, selected growth temperature P1 ＜ P2 so that the cross growth time of step 023 shortens.

It should be noted that the concrete technology of the longitudinal growth of preparation, nano wire on Seed Layer and cross growth is equal It is that those skilled in the art could be aware that.

The preparation process of wherein row of one dimensional nanometer sub-array is described below in detail.

In the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can include：

First, Figure 27 is referred to, nanometer seed precursor solution is formed on graphene film, nanometer kind is formed after drying Sub- film 301；Here, various nanometer seed presomas are different and different because of nano material, for example, zinc-oxide nano seed Precursor solution can be zinc acetate solution, and the precursor solution of nano titania seed can be titanium chloride solution etc., This is that those skilled in the art could be aware that, is repeated no more here.

Secondly, Figure 28 is referred to, nanoscale vestige is marked in nanometer seed thin film 301 using induced with laser technology, received (in Figure 28 shown in dotted line frame) induces nanometer sub-array 302 for meter level mark region.Here, the line width of nanoscale vestige can be with Equal to or more than the diameter of nanometer seed, the width of the region of nanometer sub-array 302 is equal to the line width of nanoscale vestige.Compared with Good, the line width of nanoscale vestige is no more than 5nm, and further, the line width of nanoscale vestige smaller can for example be no more than 1nm, so that the diameter of the nanometer seed for growing is no more than 5nm even 1nm, and the nano wire that goes out of subsequent growth is straight Footpath is unlikely to excessive, or even in below 5nm.It should be noted that because the nanoscale vestige of induced with laser is continuous and line It is wide ultra-fine so that seed spacing and seed diameter in nanometer sub-array are respectively less than the line width of nanoscale vestige.

Additionally, in the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can also use following step Suddenly：

First, Figure 29 is referred to, one layer of mask 401 is formed on graphene film；

Then, Figure 30 is referred to, photoetching is carried out to mask 401 and/or etching is formed one nanoscale opening 402；Here, When the material of mask 401 is photosensitivity material, one nanoscale can be etched on mask 401 using photoetching process and opened Mouth 402；When the material of mask 401 is inorganic material, can be carved using photoetching and etching technics or only with anisotropy Etching technique etches one nanoscale opening 402 on mask 401.Formation on the nanoscale opening 402, using existing Photoetching process can accomplish 10nm, and 7nm 7nm, 5nm, 3nm technologies included below use and exposure and extreme ultraviolet is repeated several times Photoetching (EUV) technology can be achieved on.Therefore, the nanoscale opening 402 of the present embodiment can accomplish the line width of below 10nm, Nanometer the diameter of seed and the diameter of spacing and the nano wire for being formed be also it is atomic small, the nano thin-film of the present embodiment and Nano net is expected to large-scale production and applies.

Finally, Figure 31 is referred to, and combines Figure 30, formed on the exposed graphene film of the institute of nanoscale opening 402 and received Rice sub-array 403.Here it is possible to using physical vaporous deposition, sol-gal process, spraying process, galvanoplastic, magnetron sputtering method Nanometer sub-array 403 is formed on the exposed graphene film of nanoscale opening institute；Or by seed solution spin coating or drop in Drying forms nanometer sub-array 403 after on the exposed graphene film of the institute of nanoscale opening 402.On nanometer sub-array 403 formation can use common process, and the precursor solution of different nano materials is used for different nano materials To prepare, usually be formed at nanometer seed precursor solution in nanoscale opening by spin-coating method, drip, through indifferent gas style Such as nitrogen drying, nanometer seed precursor film is formed, be that may be such that nanometer kind through such as not higher than 100 DEG C of temperature of low-temperature heat A nanometer sub-array is crystallized out in sub- precursor film, this is also what those skilled in the art could be aware that, repeated no more here.By Line width in nanoscale opening 402 is superfine so that the diameter and spacing of nanometer seed are all smaller, so that the nano wire for being formed Diameter, the thickness of nano thin-film and nano net thickness all in nanoscale for example in below 10nm, so as to obtain size Minimum nano net, with specific surface area higher, further suppress existing superfine nanoparticle agglomerates and duality principle Problem, therefore, the graphene-based laminated film of the present embodiment has photocatalysis efficiency and good transparency higher, Ke Yiying For transparent material in need field, such as on window, screen, clear glass, certain these transparent materials can be made It is the transparent substrates of graphene-based laminated film, not only can be with transmission applications in photovoltaic art, being also used as molecular sieve is carried out The filtering of molecular level, sterilization, elimination pernicious gas, can also carry out detection of gas and be applied in gas sensor, and application In medical treatment, biological field etc..

Although the utility model is disclosed as above with preferred embodiment, the right embodiment is illustrated only for the purposes of explanation , the utility model is not limited to, those skilled in the art is not before the utility model spirit and scope are departed from Putting can make some changes and retouching, and the protection domain that the utility model is advocated should be to be defined described in claims.

Claims (23)

1. a kind of graphene-based laminated film, it is characterised in that including：One graphene film and vertical-growth are in the graphite Nano thin-film on alkene film；The plane of the nano thin-film is vertical with the graphene film；The bottom of the nano thin-film Mutually it is bonded by chemical bond with the graphene film；The material of the nano thin-film is conductor photocatalysis material.

2. graphene-based laminated film according to claim 1, it is characterised in that the graphene film is two-layer atom The graphene film or three layers of graphene film of atomic layer of layer.

3. graphene-based laminated film according to claim 1, it is characterised in that the nano thin-film has multiple micro- engrave Hollow structure, so as to constitute nano net.

4. graphene-based laminated film according to claim 3, it is characterised in that between adjacent described micro- engraved structure Spacing be not more than 10nm.

5. graphene-based laminated film according to claim 3, it is characterised in that the nano net by nano wire perpendicular to Transparent substrates grow and the side of adjacent nanowires is in contact to form nano thin-film, then etch to form micro- vacancy section through nano thin-film Domain.

6. graphene-based laminated film according to claim 5, it is characterised in that lead between the nano wire being in contact Chemical bond is crossed mutually to be bonded.

7. graphene-based laminated film according to claim 5, it is characterised in that the diameter of nano wire is the nanometer The thickness of film.

8. graphene-based laminated film according to claim 7, it is characterised in that the thickness of the nano thin-film is not more than 10nm。

9. graphene-based laminated film according to claim 1, it is characterised in that the conductor photocatalysis material is width Gap semiconductor catalysis material.

10. graphene-based laminated film according to claim 9, it is characterised in that the wide band gap semiconducter photocatalysis Material is titanium alloy nano line and/or zinc alloy nano-wire.

11. graphene-based laminated films according to claim 1, it is characterised in that have on the graphene film many The individual nano thin-film being arranged in array.

A kind of 12. graphene-based automatically cleaning solar film batteries, it is disposed with light transmission layer, transparency electrode from top to bottom Layer and light conversion layer, incident light enter back into light conversion layer successively through light transmission layer and transparent electrode layer, and light conversion layer is absorbed Opto-electronic conversion is carried out after incident light and produce electricity；Characterized in that, the smooth transmission layer has the graphite described in claim 1 Alkenyl laminated film, wherein, the bottom of the graphene film is located at transparent electrode layer upper surface.

13. graphene-based automatically cleaning solar film batteries according to claim 12, it is characterised in that the transparent electricity Pole layer is contacted in the graphene film lower surface of light transmission layer and set using the graphene-based laminated film described in claim 1 Have a transparent substrate, the graphene film close-fitting transparent substrate layer lower surface of transparent electrode layer, transparent electrode layer it is graphene-based Nano thin-film in laminated film is located at the lower surface of its graphene film.

14. graphene-based automatically cleaning solar film batteries according to claim 12, it is characterised in that saturating in the light Cross layer top and be provided with scalable flexible and transparent protective layer, between the scalable flexible and transparent protective layer and the smooth transmission layer The scalable flexible and transparent protective layer is avoided to be in contact with the smooth transmission layer with space；It is described scalable flexible saturating The edge of bright protective layer is connected with insulating supporting structure, and the bottom part ring of insulating supporting structure is passed through around the corresponding light is arranged at The edge of layer, so as to support scalable flexible and transparent protective layer；The scalable flexible and transparent protective layer is by stretching or crimping To realize masking or exposure to the smooth transmission layer.

15. graphene-based automatically cleaning solar film batteries according to claim 14, it is characterised in that the state of curling A volume is formed including a-circle-by-a-circle rolling from inside to outside.

16. graphene-based automatically cleaning solar film batteries according to claim 14, it is characterised in that described scalable Flexible and transparent protective layer has two-layer, and ground floor is hydrophily hyaline layer, for strong less than set illumination in intensity of illumination Light transmission layer is protected during degree threshold value, so as to reduce the organic pollution in scalable flexible and transparent protective layer and light transmission layer；The Two layers is hydrophobic transparent layer, for protecting light transmission layer when ambient humidity exceedes set humidity threshold, so as to suppress Moisture enters the smooth transmission layer and enters in solar film battery；Hydrophily hyaline layer and hydrophobic transparent layer edge it Between be connected with another insulating supporting structure, for isolating and supporting two-layer hyaline layer.

17. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that described insulation Supporting construction includes upper insulating supporting structure and lower insulating supporting structure；The upper insulating supporting structure is located at the lower insulation branch The top of support structure, and the upper insulating supporting structure width of the width less than the lower insulating supporting structure so that it is lower exhausted The part that edge supporting construction is located on the inside of upper insulating supporting structure is exposed and is used to support positioned at lower insulating supporting structure One layer of scalable flexible and transparent protective layer；The top of upper insulating supporting structure is used to support on upper insulating supporting structure One layer of scalable flexible and transparent protective layer.

18. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that also with control Device, the first converter, the second converter and determining device, controller are mutually electrically connected with determining device, and determining device is mutually electrically connected with converter；Light The graphene-based laminated film of transmission layer includes：Optical detection region, intensity of illumination on solar cell is irradiated to for detecting；With And humidity search coverage, for detecting the humidity around solar cell；

Optical detection region is mutually electrically connected with the first converter, for detecting the intensity of illumination of surrounding environment and producing electric signal to be sent to The electric signal is converted to intensity of illumination data is activation to determining device by the first converter, the first converter, and determining device judges the light According to intensity data whether higher than set intensity of illumination threshold value；If it has, then determining device sends contraction signal to controller, control The device control scalable flexible and transparent protective layer processed performs crimping action；If it has not, then determining device sends stretch signal to control Device processed, the controller control scalable flexible and transparent protective layer performs stretching；

Humidity search coverage is mutually electrically connected with the second converter, for detecting the humidity of surrounding environment and producing electric signal to be sent to The electric signal is converted to humidity data and is sent to determining device by two converters, the second converter, and determining device judges the humidity data Whether higher than set humidity threshold；If it has not, then determining device sends contraction signal to controller, controller control is described can Telescopic flexible protective clear layer performs crimping action；If it has, then determining device sends stretch signal to controller, controller control The scalable flexible and transparent protective layer performs stretching.

19. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that the illumination is strong In the range of set intensity of illumination, the humidity threshold is in set humidity range for degree threshold value.

20. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that the hydrophily Hyaline layer and hydrophobic transparent layer default conditions are rolled state.

21. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that the hydrophily Hyaline layer is the graphene film of individual layer atomic layer.

22. graphene-based automatically cleaning solar film batteries according to claim 16, it is characterised in that the hydrophobicity Hyaline layer is two-layer or three layers of graphene film of atomic layer.

23. graphene-based automatically cleaning solar film batteries according to claim 12, it is characterised in that the light conversion Layer is dye-sensitized layer, also has bottom electrode layer in light conversion layer bottom.