CN103787259A - Flexible microstructure based on graphene and used for obtaining weak energy and manufacturing method thereof - Google Patents
Flexible microstructure based on graphene and used for obtaining weak energy and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a flexible microstructure based on graphene and used for obtaining weak energy and a manufacturing method thereof. The flexible microstructure is a layered structure and comprises a first-part structure and a second-part structure. The first-part structure comprises a flexible substrate, a graphene layer formed on the flexible substrate, a zinc oxide nanowire layer grown on the graphene layer and an extraction electrode layer on the graphene layer. The second-part structure comprises a flexible substrate, a graphene layer and an extraction electrode layer, wherein the graphene layer and the extraction electrode layer are formed on the flexible substrate. The first-part structure and the second-part structure are fixed together and the flexible substrates are located on outermost portion. At least one layer of grapheme / a zinc oxide nanowire layer is formed on the zinc oxide nanowire layer. The flexible microstructure based on the graphene and used for obtaining the weak energy and the manufacturing method of the flexible microstructure have the advantages that serving as electrode materials, the graphene layers improve the charge collecting speed, greatly improve the reliability of a device and prolong the service life of the device; controllable growth of zinc oxide nanowires can greatly improve the piezoelectric property, and due to the ingeniously designed series-connection parallel-connection structure, the function requirements of different self-driving micro-nanometer systems can be met.
Description
Technical field
The present invention relates to a kind of flexible micro-structural and manufacture method thereof, be specifically related to a kind of build based on zinc oxide nanowire and graphene film for obtaining flexible micro-structural and the manufacture method thereof of faint energy, belong to faint energy harvesting technical field.
Background technology
Along with the development of micro-nano system, the size of micro-nano system is more and more less, and what limit whole system size in the future is power supply rather than other devices; Realize in the future the number of omnibearing monitoring micro-nano system used and density suitable great again, and the applied environment of these removable systems is complicated and changeable, the scheme of utilization replacing battery and traditional energy harvesting technology can not meet the functional requirement of micro-nano system.Therefore, had self-driven concept, it is to utilize the energy of collecting from environment at all, drive these micro-nano systems by power conversion, realize power self-sufficiency, thereby solve the powerup issue of micro-nano system, realize the microminiaturization of sensor and the extensive distribution of sensing network.Now self-driven concept has become the research field that the world enlivens very much.
2004, the physicist An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu successfully isolated Graphene in experiment from graphite.Since Graphene is found since then, Chinese scholars has been carried out extensive and deep research to it.The new method of preparing Graphene also emerges in an endless stream.The performances such as electricity based on Graphene excellence, mechanics, calorifics, also constantly extend its further application study.But the preparation technology of Graphene and IC technique are not very compatible, have limited its application.
2012, Shenyang material science country (associating) laboratory advanced Carbon Materials research department delivered the harmless transfer method of a kind of bubbling based on electrochemical gas intercalation, Graphene can be transferred in any substrate.The realization of Graphene transfer techniques has further expanded the range of application of Graphene.
In the application study report of Graphene, have no Graphene electricity mechanical property is combined to the correlative study bibliographical information that is further applied to micro-nano system.Therefore the excellent electricity of Graphene and mechanical property can be applied in faint energy harvesting micro-structural simultaneously and improve device performance.
Summary of the invention
The object of the present invention is to provide a kind of based on Graphene for obtaining flexible micro-structural and the manufacture method thereof of faint energy, concrete, electrode material using Graphene as energy converter and as bear extraneous load structural material, utilize the novel energy converter structure of zinc oxide nanowire as functional material, in order to obtain faint nonelectrical energy and high efficiency to be converted to electric energy, multiple power conversion core textures can be connected or the overlaying structure that forms in parallel, reach the power demands of self-driven micro-nano system.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
, it is characterized in that for obtaining a flexible micro-structural for faint energy based on Graphene, aforementioned flexible micro-structural is layer structure, and is divided into two parts, and Part I structure and Part II structure are secured together, wherein,
Consisting of of Part I structure: the first flexible substrate, be formed at the first one-sided graphene layer of aforementioned the first flexible substrate, grow in the first zinc oxide nanowire layer on aforementioned the first graphene layer, on aforementioned the first graphene layer, be also formed with the first extracting electrode layer, aforementioned the first extracting electrode layer comprises: gold layer and copper cash;
Consisting of of Part II structure: the second flexible substrate, be formed on the second one-sided graphene layer of aforementioned the second flexible substrate, on aforementioned the second graphene layer, be also formed with the second extracting electrode layer, aforementioned the second extracting electrode layer comprises: gold layer and copper cash;
Aforementioned the first flexible substrate and the second flexible substrate are all positioned at outermost layer.
Aforesaid flexible micro-structural, is characterized in that, in Part I structure, is also formed with Graphene/zinc oxide nanowire layer, the number of plies >=1 of aforementioned Graphene/zinc oxide nanowire layer on aforementioned the first zinc oxide nanowire layer.
Aforesaid flexible micro-structural, is characterized in that, the zinc oxide nanowire vertical-growth in zinc oxide nanowire layer is on graphene layer.
Aforesaid flexible micro-structural, is characterized in that, aforementioned the first flexible substrate and the second flexible substrate are any one in PET, PI and PEN.
Aforesaid flexible micro-structural, is characterized in that, in the first extracting electrode layer and the second extracting electrode layer, the thickness of aforementioned gold layer is 50-100nm, and the diameter of aforementioned copper cash is 0.03mm.
Manufacture the method that is used for the flexible micro-structural of obtaining faint energy based on Graphene, it is characterized in that, comprise the following steps:
(1) in the first flexible substrate, shift the first graphene layer;
(2) at one end of the first graphene layer plated with gold layer, and draw output lead on gold layer, form the first extracting electrode layer;
(3) the first zinc oxide nanowire layer of growing on the first graphene layer, obtains zinc oxide nanowire/Graphene/flexible substrate;
(4) in the second flexible substrate, shift the second graphene layer;
(5) at one end of the second graphene layer plated with gold layer, and draw output lead on gold layer, form the second extracting electrode layer, obtain Graphene/flexible substrate;
(6) exert pressure by normal temperature physics, the zinc oxide nanowire layer of zinc oxide nanowire/Graphene/flexible substrate is combined with the graphene layer of Graphene/flexible substrate, and with adhesive tape binding and protection.
The method of the flexible micro-structural of aforesaid manufacture, is characterized in that, the step of the first zinc oxide nanowire layer of growing on the first graphene layer is:
(1) on the first graphene layer, make the Seed Layer of zinc oxide nanowire;
(2) first flexible substrate with the first graphene layer is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, the first graphene layer is downward, under the condition of heating, growth obtains the first zinc oxide nanowire layer, obtains zinc oxide nanowire/Graphene/flexible substrate.
The method of the flexible micro-structural of aforesaid manufacture, is characterized in that, is also included in the step that obtains Graphene/zinc oxide nanowire layer on the first zinc oxide nanowire layer:
On the first zinc oxide nanowire layer, shift graphene layer, then on graphene layer, make again the Seed Layer of zinc oxide nanowire, flexible substrate is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, graphene layer is downward, under the condition of heating, regrow zinc oxide nanowire layer, obtain Graphene/zinc oxide nanowire layer; So circulation, obtains at least one layer graphene/zinc oxide nanowire layer.
The method of the flexible micro-structural of aforesaid manufacture, is characterized in that, aforementioned two hydration zinc acetates are 1:1 with the ratio of the molar concentration of hexamethylenetetramine, and molar concentration scope is 10-50mmol/L.
The method of the flexible micro-structural of aforesaid manufacture, is characterized in that, the growth temperature of aforementioned zinc oxide nanowire layer is 90 ℃.
Usefulness of the present invention is: first the environment for use of this energy converter has been expanded in the selection of flexible substrate, can make device microminiaturization, and weight reduction greatly, reduces costs; Secondly, graphene layer, as electrode material, has not only improved the gathering speed of electric charge, what is more important, the Zinc oxide nanowire electric generator relatively having occurred, reliability and the service life that can greatly improve device; Finally, the controllability growth of zinc oxide nanowire can improve its piezoelectric property greatly, by the series parallel structure of ingehious design, can meet the functional requirement of different self-driven micro-nano systems, greatly expand the application for the flexible micro-structural of faint energy harvesting based on Graphene, can also well meet the difference in functionality demand of micro-nano system by optimal design; Used symmetrical structure, certain structures can be prepared simultaneously, has reduced making flow process, and nano generator is easily made, and cost is low and improved production efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of a specific embodiment of flexible micro-structural of the present invention;
Fig. 2 is the schematic flow sheet of the flexible micro-structural shown in shop drawings 1;
Fig. 3 is the structural representation of another specific embodiment of flexible micro-structural of the present invention;
Fig. 4 is the structural representation of the 3rd specific embodiment of flexible micro-structural of the present invention.
The implication of Reference numeral in figure: 11-flexible substrate, 12-flexible substrate, 21-graphene layer, 22-graphene layer, 31-extracting electrode layer, 32-extracting electrode layer, 4-the first zinc oxide nanowire layer, 5-Graphene/zinc oxide nanowire layer.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is done to concrete introduction.
First, introduce and the present invention is based on Graphene for obtaining the flexible micro-structural of faint energy.
With reference to Fig. 1, the flexible micro-structural that is used for obtaining faint energy based on Graphene of the present invention, it is a layer structure, and is divided into two parts, Part I structure and Part II structure are secured together.Introduce respectively Part I structure and Part II structure below.
Consisting of of Part I structure: the first flexible substrate 11, be formed at the first one-sided graphene layer 21 of the first flexible substrate 11, grow in the first zinc oxide nanowire layer 4 on the first graphene layer 21.Wherein, be also formed with the first extracting electrode layer 31 on the first graphene layer 21, this first extracting electrode layer 31 comprises: gold layer and copper cash, and the thickness of gold layer is preferably 50-100nm, and the diameter of copper cash is preferably 0.03mm.
Consisting of of Part II structure: the second flexible substrate 12, be formed at the second one-sided graphene layer 22 of the second flexible substrate 12, on the second graphene layer 22, be also formed with the second extraction electrode 32, this second extraction electrode 32 comprises: gold layer and copper cash, the thickness of gold layer is preferably 50-100nm, and the diameter of copper cash is preferably 0.03mm.
Part I structure and Part II structure are secured together and obtain flexible micro-structural of the present invention, and wherein, the first flexible substrate 11 and the second flexible substrate 12 are all positioned at outermost layer.
In the present invention, the first graphene layer 21 and the second graphene layer 22 are as upper/lower electrode layer, and the first zinc oxide nanowire layer 4 is as functional layer.Graphene layer, as electrode material, has not only improved the gathering speed of electric charge, what is more important, the Zinc oxide nanowire electric generator relatively having occurred, reliability and the service life that can greatly improve device.
As the preferred scheme of one, with reference to Fig. 3 and Fig. 4, on the first zinc oxide nanowire layer 4, be also formed with Graphene/zinc oxide nanowire layer 5, and the number of plies >=1 of Graphene/zinc oxide nanowire layer 5, that is to say, in flexible micro-structural, zinc oxide nanowire layer can be both individual layer (shown in Fig. 1), also can be double-deck (shown in Fig. 3), can also be three layers (shown in Fig. 4) or more than three layers, the concrete number of plies is selected according to the needs of actual conditions.
The controllability growth of zinc oxide nanowire can improve its piezoelectric property greatly, by the cascaded structure of ingehious design, can meet the functional requirement of different self-driven micro-nano systems, greatly expand the application for the flexible micro-structural of faint energy harvesting based on Graphene, can also well meet the difference in functionality demand of micro-nano system by optimal design.
More preferably, the zinc oxide nanowire vertical-growth in zinc oxide nanowire layer is on graphene layer.
In the present invention, the first flexible substrate 11 and the second flexible substrate 12 are preferably PET(PETG), PI(polyimides) and PEN(PEN) in any one.The environment for use of this energy converter has been expanded in the selection of flexible substrate, can make device microminiaturization, and weight reduction greatly, reduces costs.
Next,, with reference to Fig. 2, introduce the method that is used for the flexible micro-structural of obtaining faint energy based on Graphene of manufacturing.
Embodiment 1
Zinc oxide nanowire layer is individual layer.
Manufacture method of the present invention comprises the following steps:
1, each one deck graphene layer, i.e. the first graphene layer 21 and the second graphene layer 22 of shifting in the first flexible substrate 11 and the second flexible substrate 12.Specific as follows:
Be taken at the upper graphene film of having grown of copper sheet (other substrates such as platinum, nickel, ruthenium, iridium etc. all can); protect at the one side spin coating PMMA that has Graphene, then copper sheet is put into FeCl3 solution corrode, after 4 hours; copper is corroded, then transfers in deionized water and clean.The last surperficial PMMA of removal that soaks in acetone, can transfer to graphene film in the first flexible substrate 11 and the second flexible substrate 12, obtains Graphene/PET substrate.
Wherein, the first flexible substrate 11, the second flexible substrate 12 are PET film, are of a size of 3.5cm × 2cm; The first graphene layer 21 and the second graphene layer 22 are individual layer, and size is identical with the second flexible substrate 12 with the first flexible substrate 11, are all 3.5cm × 2cm.
Adopt PET film as substrate, it has good mechanical property, impact strength is 3-5 times of other films, also have that good chemical stability, folding resistance are good, wearability, electrical insulating property, resistance to fatigue resistance, good stability of the dimension etc., but in the present invention, also can adopt other resilient substrates, for example PI(polyimides), PEN(PEN), as long as extraneous mechanical energy can be converted into elastic potential energy and pass to zinc oxide nanowire.
2, utilize respectively hot vapour deposition method plated with gold layer in one end of the first graphene layer 21 and the second graphene layer 22, gold layer is of a size of 2cm × 0.5cm, and thickness is 50-100nm.
3, on gold layer, draw output lead respectively, concrete, with silver slurry on gold layer fixed copper wire as output, copper conductor size: diameter is in 0.03mm left and right, length 5cm left and right, thereby form the first extracting electrode layer 31 and the second extracting electrode layer 32.
4, get the first flexible substrate 11 with copper conductor, the Seed Layer of making zinc oxide nanowire on the first graphene layer 21.Specific as follows:
A certain amount of two hydration zinc acetates [Zn (CH3COO) 2 2H2O] are dissolved in to ethanol, are mixed with the solution of 5mmol/L.This solution is spun on to Graphene/PET substrate (1000 revs/min of rotary speeies), repeats 3 to 5 times, make the Seed Layer that is applicable to growth.
5, Graphene/PET the substrate that has Seed Layer of making is swum in to the surface of the mixed aqueous solution (mixed aqueous solution is contained in autoclave) of two hydration zinc acetates and hexamethylenetetramine, aufwuchsplate graphene layer is (to avoid the ZnO crystal grain in solution to be deposited on the mixed and disorderly unordered structure of its surface generation) downwards, autoclave is put into 90 ℃ of vacuum drying baking boxes to be heated, grow and after 4 hours, sample is taken out, repeatedly rinse and natural drying in air by deionized water, growth obtains the first zinc oxide nanowire layer 4, obtain zinc oxide nanowire/Graphene/PET substrate.
Wherein, the preparation method of mixed aqueous solution: take respectively two appropriate hydration zinc acetate [Zn (CH with electronic scale
3cOO)
22H
2o] and hexamethylenetetramine [C
6h
12n
4], put into teflon-lined autoclave, and add 80ml deionized water as solvent, zinc acetate and the hexamethylenetetramine aqueous solution of molar concentration (25mmol/L) such as be mixed with.
It should be noted that, zinc acetate and hexamethylenetetramine be molar concentration within the scope of 10-50mmol/L, all can realize the growth of zinc oxide nanowire layer.
Graphene/PET substrate is swum in to zinc acetate and hexamethylenetetramine aqueous solution surface, than the one side that there is no Graphene of Graphene/PET substrate being attached to the container bottom of the above-mentioned aqueous solution or the one side that there is no Graphene of Graphene/PET substrate being attached to the situation on the chamber wall of the above-mentioned aqueous solution, can effectively improve the adhesion between the graphene layer on grown zinc oxide nanowire and substrate, make zinc oxide nanowire difficult drop-off.
6, exert pressure by normal temperature physics; the first zinc oxide nanowire layer 4 of zinc oxide nanowire/Graphene/PET substrate is combined with the second graphene layer 22 of Graphene/PET substrate; guarantee in conjunction with closely, finally use adhesive tape (PET adhesive tape, PI adhesive tape all can) binding and protection.
Embodiment 2
Zinc oxide nanowire layer is multilayer.
Manufacture method of the present invention comprises the following steps:
1, each one deck graphene layer, i.e. the first graphene layer 21 and the second graphene layer 22 of shifting in the first flexible substrate 11 and the second flexible substrate 12.Specific as follows:
Be taken at the upper graphene film of having grown of copper sheet (other substrates such as platinum, nickel, ruthenium, iridium etc. all can); protect at the one side spin coating PMMA that has Graphene, then copper sheet is put into FeCl3 solution corrode, after 4 hours; copper is corroded, then transfers in deionized water and clean.The last surperficial PMMA of removal that soaks in acetone, can transfer to graphene film in the first flexible substrate 11 and the second flexible substrate 12, obtains Graphene/PET substrate.
Wherein, the first flexible substrate 11 and the second flexible substrate 12 are PET film, are of a size of 3.5cm × 2cm; In addition, the first flexible substrate 11 and the second flexible substrate 12 can also be selected PI or PEN; Now the first graphene layer 21 and the second graphene layer 22 are individual layer, and size is identical with the second flexible substrate 12 with the first flexible substrate 11, are all 3.5cm × 2cm.
2, utilize respectively hot vapour deposition method plated with gold layer in one end of the first graphene layer 21 and the second graphene layer 22, gold layer is of a size of 2cm × 0.5cm, and thickness is 50-100nm.
3, on gold layer, draw output lead respectively, concrete, with silver slurry on gold layer fixed copper wire as output, copper conductor size: diameter is in 0.03mm left and right, length 5cm left and right, thereby form the first extracting electrode layer 31 and the second extracting electrode layer 32.
4, get the first flexible substrate 11 with copper conductor, the Seed Layer of making zinc oxide nanowire on the first graphene layer 21.Specific as follows:
By the two hydration zinc acetate [Zn (CH of 5mmol/L
3cOO)
22H
2o] ethanolic solution is spun on Graphene/PET substrate (1000 revs/min of rotary speeies), repeats 3 to 5 times, makes the Seed Layer that is applicable to growth.
5, Graphene/PET the substrate that has Seed Layer of making is swum in to the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, and (mixed aqueous solution is contained in autoclave, the molar concentration of zinc acetate and hexamethylenetetramine is 25mmol/L) surface, aufwuchsplate graphene layer is downward, autoclave is put into 90 ℃ of vacuum drying baking boxes to be heated, grow and after 4 hours, sample is taken out, repeatedly rinse and natural drying in air by deionized water, growth obtains the first zinc oxide nanowire layer 4, obtain zinc oxide nanowire/Graphene/PET substrate.
6, after obtaining the first zinc oxide nanowire layer 4, on the first zinc oxide nanowire layer 4, shift graphene layer, then on graphene layer, make again the Seed Layer of zinc oxide nanowire, substrate is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, graphene layer is downward, the second layer zinc oxide nanowire layer of growing under the heating condition of 90 ℃, obtains Graphene/zinc oxide nanowire layer 5.
7, after obtaining second layer zinc oxide nanowire layer, after obtaining Graphene/zinc oxide nanowire layer 5, on second layer zinc oxide nanowire layer, shift again graphene layer, then on graphene layer, make again the Seed Layer of zinc oxide nanowire, substrate is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, graphene layer is downward, and under the heating condition of 90 ℃, three layers of zinc oxide nanowire layer of growth regulation, obtain Graphene/zinc oxide nanowire layer again.
So the transfer of carrying out Graphene of circulation and the growth of zinc oxide nanowire layer, can form cascaded structure, thereby further improve the generated energy of graphene-based flexible nano generator.
Adopt the above-mentioned method providing can obtain Graphene/zinc oxide nanowire layer of 50 layers of left and right.
8, exert pressure by normal temperature physics, the zinc oxide nanowire layer in the first flexible substrate 11 is combined with the second graphene layer 22 in the second flexible substrate 12, guarantee in conjunction with closely, finally with adhesive tape binding and protection.
By the cascaded structure of ingehious design, can meet the functional requirement of different self-driven micro-nano systems, greatly expand the application for the flexible micro-structural of faint energy harvesting based on Graphene, can also well meet the difference in functionality demand of micro-nano system by optimal design.
It should be noted that, above-described embodiment does not limit the present invention in any form, and all employings are equal to replaces or technical scheme that the mode of equivalent transformation obtains, all drops in protection scope of the present invention.
Claims (10)
1. the flexible micro-structural that is used for obtaining faint energy based on Graphene, is characterized in that, described flexible micro-structural is a layer structure, and is divided into two parts, and Part I structure and Part II structure are secured together, wherein,
Consisting of of Part I structure: the first flexible substrate, be formed at the first one-sided graphene layer of described the first flexible substrate, grow in the first zinc oxide nanowire layer on described the first graphene layer, on described the first graphene layer, be also formed with the first extracting electrode layer, described the first extracting electrode layer comprises: gold layer and copper cash;
Consisting of of Part II structure: the second flexible substrate, be formed on the second one-sided graphene layer of described the second flexible substrate, on described the second graphene layer, be also formed with the second extracting electrode layer, described the second extracting electrode layer comprises: gold layer and copper cash;
Described the first flexible substrate and the second flexible substrate are all positioned at outermost layer.
2. flexible micro-structural according to claim 1, is characterized in that, in Part I structure, is also formed with Graphene/zinc oxide nanowire layer, the number of plies >=1 of described Graphene/zinc oxide nanowire layer on described the first zinc oxide nanowire layer.
3. flexible micro-structural according to claim 1 and 2, is characterized in that, the zinc oxide nanowire vertical-growth in zinc oxide nanowire layer is on graphene layer.
4. flexible micro-structural according to claim 1, is characterized in that, described the first flexible substrate and the second flexible substrate are any one in PET, PI and PEN.
5. flexible micro-structural according to claim 1, is characterized in that, in the first extracting electrode layer and the second extracting electrode layer, the thickness of described gold layer is 50-100nm, and the diameter of described copper cash is 0.03mm.
6. manufacture the method that is used for the flexible micro-structural of obtaining faint energy based on Graphene, it is characterized in that, comprise the following steps:
(1) in the first flexible substrate, shift the first graphene layer;
(2) at one end of the first graphene layer plated with gold layer, and draw output lead on gold layer, form the first extracting electrode layer;
(3) the first zinc oxide nanowire layer of growing on the first graphene layer, obtains zinc oxide nanowire/Graphene/flexible substrate;
(4) in the second flexible substrate, shift the second graphene layer;
(5) at one end of the second graphene layer plated with gold layer, and draw output lead on gold layer, form the second extracting electrode layer, obtain Graphene/flexible substrate;
(6) exert pressure by normal temperature physics, the zinc oxide nanowire layer of zinc oxide nanowire/Graphene/flexible substrate is combined with the graphene layer of Graphene/flexible substrate, and with adhesive tape binding and protection.
7. the method for the flexible micro-structural of manufacture according to claim 6, is characterized in that, the step of the first zinc oxide nanowire layer of growing on the first graphene layer is:
(1) on the first graphene layer, make the Seed Layer of zinc oxide nanowire;
(2) first flexible substrate with the first graphene layer is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, the first graphene layer is downward, under the condition of heating, growth obtains the first zinc oxide nanowire layer, obtains zinc oxide nanowire/Graphene/flexible substrate.
8. the method for the flexible micro-structural of manufacture according to claim 6, is characterized in that, is also included in the step that obtains Graphene/zinc oxide nanowire layer on the first zinc oxide nanowire layer:
On the first zinc oxide nanowire layer, shift graphene layer, then on graphene layer, make again the Seed Layer of zinc oxide nanowire, flexible substrate is swum in to the surface of the mixed aqueous solution of two hydration zinc acetates and hexamethylenetetramine, graphene layer is downward, under the condition of heating, regrow zinc oxide nanowire layer, obtain Graphene/zinc oxide nanowire layer; So circulation, obtains at least one layer graphene/zinc oxide nanowire layer.
9. according to the method for the flexible micro-structural of the manufacture described in claim 6,7,8 any one, it is characterized in that, described two hydration zinc acetates are 1:1 with the ratio of the molar concentration of hexamethylenetetramine, and molar concentration scope is 10-50mmol/L.
10. according to the method for the flexible micro-structural of the manufacture described in claim 6,7,8 any one, it is characterized in that, the growth temperature of described zinc oxide nanowire layer is 90 ℃.
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