CN104802350A - Preparation method of intermediate film, intermediate film and nano-generator prepared from intermediate film - Google Patents
Preparation method of intermediate film, intermediate film and nano-generator prepared from intermediate film Download PDFInfo
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- CN104802350A CN104802350A CN201510091301.4A CN201510091301A CN104802350A CN 104802350 A CN104802350 A CN 104802350A CN 201510091301 A CN201510091301 A CN 201510091301A CN 104802350 A CN104802350 A CN 104802350A
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Abstract
The invention provides a preparation method of an intermediate film, the intermediate film and a nano-generator prepared from the intermediate film. The intermediate film of the nano-generator is directly prepared from a metal grid template, the condition that an etched silicon wafer is used as the template is avoided, the film template with metal grids is not required to be etched, the preparation process is simple, the preparation technology of the intermediate film is simplified, and the preparation process is simple and easy to realize. Besides, the structure and the size of the metal grids of the metal grid template are easy to control, and molding is easy to control; the metal grid template can be recycled; meanwhile, the metal grids can be used as an electrode of the nano-generator due to the electrical conductivity, so that the electrode reconfiguration procedure in the prior art is simplified. The intermediate film can be enlarged and produced in batches. The nano-generator prepared from the intermediate film has higher output voltage.
Description
Technical field
The present invention relates to a kind of preparation method of film between two parties, and the film between two parties obtained according to preparation method and use the nano generator of this film between two parties.
Background technology
Along with the develop rapidly of electronic technology, various electronic product constantly occurs, for it provides the rechargeable battery of power supply also in update rapidly.But along with the appearance of nanosensor system and the expansion of application thereof, in micro-nano system application, particularly for the lasting detection system of environmental system or body system, lack continued power device.Nanometer generating device, with the self power generation of its uniqueness and self-driven character, can play critical effect, more and more receive the concern of researcher in nano-device or nanosystems device.2006, professor Wang Zhonglin of the georgia ,u.s.a Institute of Technology first successful design went out piezoelectric nano generator, and thinking has been opened up in the research and development for nm regime electric supply installation.Afterwards, along with the nanometer generating device constantly studied intensively based on piezo-electric effect, friction effect of various countries scientific research personnel is succeeded in developing in succession.
The nano generator developed based on friction effect, comprises the first electrode layer, between two parties frictional layer and the second electrode lay.Application number be 201210160542.6 Chinese invention patent document disclose a kind of friction generator, this friction generator between two parties film has micro-nano ridge design, research shows that film has micro-nano ridge design between two parties, and the nano friction generator output voltage of its assembling and output current are apparently higher than the nano generator not having the film between two parties of micro-structural to assemble.This publication disclose a kind of preparation method of film between two parties, its step is the silicon template of first construction drawing shape, use the method for photoetching to make regular figure on surface, carry out anisotropic etching by the technique of wet etching, carve the rectangular pyramid array architecture of matrix; The cubic array structure that isotropic etching goes out spill is carried out by the technique at dry quarter; The template of having carved cleans up in acetone and isopropyl alcohol, carries out silanization treatment at the atmosphere of trim,ethylchlorosilane.Prior art uses high molecular polymer coating process to prepare film between two parties, and method for be coated with high molecular polymer on base material.The coating process of high molecular polymer is: first high polymer presoma and curing agent are proportionally mixed.Then mixture is coated on the silicon template surface of above-mentioned preparation, after Vacuum Degassing Process, adopts the mode of rotary coating to be removed by mixture unnecessary for silicon face, form the macromolecule liquid film of thin layer.Whole template is solidified 1h under 85 DEG C of environment, later layer have uniformly specific microstructure display polymeric membrane just can peel off from template, obtain film between two parties.The method make between two parties film time need adopt silicon masterplate, silicon template making technique is complicated, and cost intensive, causes the complicated process of preparation of film between two parties, be unsuitable for large-scale production.
Summary of the invention
The object of the invention is to overcome above-mentioned prior art Problems existing, provide the preparation method of a kind of nano generator film between two parties, the method technique is simple, can adapt to the production of scale.
Another technical problem to be solved by this invention is to provide this nano generator film between two parties, and this film can amplify, mass production.
The 3rd technical problem that the present invention also will solve is to provide a kind of nano generator, and this generator has higher output voltage.
The adopted technical scheme that solves the problem is:
A nanometer engine preparation method for film between two parties, comprises the following steps:
A), on base film prepare metal grill, with absolute ethyl alcohol or acetone cleaning, obtain aperture 10-100 micron, the metal grill template of netting twine height 2-10 micron, netting twine width 10-40 micron;
B, in metal grill template, be coated with the mixture that is made up of high molecular polymer and curing agent of one deck;
C), at 60 ~ 100 DEG C, solidify 20 ~ 60 minutes;
D, stripping; Obtain film between two parties.
Described high molecular polymer is one or more in dimethyl silicone polymer, Kynoar, polymethyl methacrylate, polystyrene, Merlon and PETG;
Described curing agent is silane coupler;
The mass ratio of described high molecular polymer and curing agent is 100:1 ~ 100:20.
Above-mentioned preparation method, described metal grill is prepared by the way of silver halide exposure imaging.
Above-mentioned preparation method, described metal grill contains 50 ~ 100% silver medals.
Above-mentioned preparation method, described metal grill cross section is circle, square, rectangle, hexagon, triangle.
Above-mentioned preparation method, the mass ratio of described high molecular polymer and curing agent is 100:5 ~ 100:10.
Above-mentioned preparation method, described metal grill resistance is 150 ± 50m Ω/.
One is film between two parties, and described film between two parties comprises body and bossing, and the gross thickness of film is 50-500 micron between two parties.
A kind of nano generator, described nano generator comprises the obtained film between two parties of said method.
Above-mentioned nano generator, described nano generator also comprises metal grid electrode.
Above-mentioned nano generator, described nano generator sets gradually the first electrode layer, between two parties film, the second electrode lay and supporting layer, and described second electrode is metal grill template.
beneficial effect:
1. the present invention uses metal grill template as the preparation template of film between two parties, instead of prior art uses silicon chip etching as the preparation technology of template, do not need to etch on silicon chip, simplify the preparation technology of film between two parties, and preparation process is simple, and metal grill can reuse as template;
2. use the method for silver emulsion to prepare metal grill, structure and the size of metal grill easily control, and shaping easy control, and required to prepare instrument simple;
3., because metal grill has electric conductivity, metal grill template of the present invention can also use as the electrode of nano generator.
4. nano generator of the present invention adopts the film between two parties of metal grill Template preparation and adopts the electrode of metal grill Template preparation, and preparation process is more easy.
Accompanying drawing illustrates:
Fig. 1 is the micro-image of metal grill template of the present invention;
Fig. 2 is the micro-image of film between two parties prepared by the present invention;
Fig. 3 and Fig. 4 is the nano generator structural representation utilizing the present invention's film assembling between two parties;
Fig. 5 is arch nano generator schematic diagram.
In figure, each label is expressed as: 1-first electrode layer, and 2-is film between two parties, 3-second electrode, 4-supporting layer.
Detailed description of the invention
Film between two parties of the present invention is applicable to friction-type nano generator, and the general structure of friction-type nano generator is followed successively by the first electrode layer 1, between two parties film 2, the second electrode lay 3 and supporting layer 4.First electrode, supporting layer and between two parties film form upper strata, the second electrode and supporting layer form lower floor.The edge, two, left and right of bilevel correspondence is bonded together, and centre reserves gap, and gap is arc, and maximum height is 5-20mm.For ensureing the gap between levels, the wide 2-5mm of side ratio lower floor on upper strata, supporting and embodying use PET.
The preparation method of film between two parties of the present invention is:
A) on base film, prepare metal grill, with absolute ethyl alcohol or acetone cleaning, obtain aperture 10-100 micron, grid height 2-10 micron, percent opening are the metal grill template of 50 ~ 90%;
B) in metal grill template, the mixture that one deck is made up of high molecular polymer and curing agent is coated with;
C) at 60 ~ 100 DEG C, solidify 20 ~ 60 minutes, preferably at 80 DEG C, solidify 30 minutes;
D) peel off; Obtain film between two parties,
Described high molecular polymer is one or more in dimethyl silicone polymer, Kynoar, polymethyl methacrylate, polystyrene, Merlon and PETG;
Described curing agent is silane coupler; The source of the present invention to described curing agent does not have special restriction, adopt curing agent well known to those skilled in the art, as its commercial goods can be adopted, in an embodiment of the present invention, curing agent preferably uses the silane coupled agent series products of Zhejiang Xinan Chemical Industry Group Co.Ltd; The mass ratio of described high molecular polymer and curing agent is 100:1 ~ 100:20.
Described base film can be the macromolecular materials such as PETG, polyimides, polyethylene, preferred PETG (PET) film, thickness can select the PET film of 25 ~ 175 micron thickness, consider that it needs certain deflection as during electrode support, the preferably PET film of 75 ~ 150 micron thickness simultaneously.
Base material is prepared metal grill obtain metal grill template and can adopt any known method, the method of preferred use silver emulsion exposure imaging, the way of silver halide exposure imaging is adopted to prepare metal grill, this is the metal grill controlled shape owing to obtaining by the method, width and the thickness of grid lines easily control, aperture opening ratio easily controls, and method is simple.After obtaining silver-colored grid by the way of silver halide exposure imaging, with the metal grill obtained for template, by modes such as chemical platings, silver-colored grid can be coated with other metals, as the metal of the good conductivity such as copper, gold, also can directly as metal grill template.Metal grill template of the present invention need meet aperture 10-100 micron, and grid height 2-10 micron, percent opening are the requirement of 50 ~ 90%.Make between two parties film time, the bossing of the film between two parties that the hole of metal grill template is corresponding.If metal grill template of the present invention is just as the template use of film between two parties, too much consideration is not done to the resistance of metal grill template, if both as the template of film between two parties, the electrode again as nano generator had used, sheet resistance preferably 150 ± 50m Ω/ of metal grill template of the present invention.
The cross section of the metal grill in metal grill template of the present invention can have any shape, as circle, square, rectangle, hexagon, triangle, and trapezoidal, polygon and other are irregularly shaped etc.
Film between two parties of the present invention is formed by the mixture solidified be made up of liquid macroimolecule polymer and LCM be coated in metal grill template, described high molecular polymer is dimethyl silicone polymer (PDMS), Kynoar (PVDF), polymethyl methacrylate (PMMA), polystyrene (PS), Merlon (PC), the one in polymeric liquid crystal copolymer (LCP) or PETG (PET).
Described high molecular polymer and the mass ratio of curing agent are 100:1 ~ 100:20, preferred 100:5 ~ 100:10.The mass ratio of high molecular polymer and curing agent is within the scope of this, and mixture viscosity is moderate, and bubble is few, is convenient to coating, and high molecular polymer hardening time and good film-forming property.
Film between two parties of the present invention controls within the scope of 60 ~ 100 DEG C in temperature, dry 30 ~ 60 minutes.
The film between two parties that the present invention obtains comprises body and bossing, and the gross thickness of film is thickness is between two parties 50-500 micron, and height of projection is consistent with the height of line of metal grill template.
First electrode of nano generator of the present invention and the second electrode can select metal, metal-oxide film, metal grill template, and be preferably ito thin film, nano silver wire film and silver-colored net template, the preferred 5-50 micron of thickness, resistance is 150 ± 50m Ω/ preferably.
Film between two parties of the present invention is applied on nanometer engine, be aided with the first electrode layer, the second electrode lay and supporting layer, adopt automatic dotting device (the Hua Yichuanhong company RS-5610H) pressing after improving, oscillograph (Deco skill infiniivision 2000X) display translation voltage and current.Result shows, and nano generator output voltage 80-120 lies prostrate, output current 2-10 microampere, and repeated presses 30,000 ten thousand performances are unattenuated.Its average output power is than the raising more than 50% not with micro-structural.
Embodiment 1:
The preparation of 1-1, between two parties film, in the PET film of 125 micron thickness, is coated with the silver emulsion of 10 micron thickness, and after exposure imaging, with washes of absolute alcohol, obtaining live width is 10 microns, and distance between centers of tracks is 70 microns, and line height is the silver-colored net template of 8 microns;
On the silver-colored grid of above-mentioned silver-colored net template, be coated with by high molecular polymer PDMS(DOW CORNING 184) and the coating fluid of silane coupler, the mass percent of high molecular polymer and curing agent is 10:1,
At 80 DEG C, solidify 30 minutes;
Peeled off from silver-colored grid by the film of completion of cure, obtaining gross thickness is 150 microns, and height of projection is the film between two parties 1 of 8 microns.
The preparation of 1-2, nano generator
Utilize 3 nano generators assembled by reference to the accompanying drawings of the PDMS film with micro-structural prepared.Described nano generator comprises the first electrode layer 1, between two parties film 2, the second electrode lay 3 and electrode backing layer 4.First, second electrode layer all comprises the electrode of the silver-colored grid protocol on PET and PET support.Be pasted onto on the PET of the first electrode by the body of the PDMS film prepared, projection is just to the second electrode, and be the nano generator shown in accompanying drawing 5 by the first electrode, between two parties film, the second electrode assembling, the arch nano generator spacing of generator is 10 millimeters.
Adopt automatic dotting device (the Hua Yichuanhong company RS-5610H) pressing after improving, oscillograph (Deco skill infiniivision 2000X) display translation voltage and current.Result shows, nano generator output voltage 80 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 2
With embodiment 1, embodiment 2 use silver-colored grid parameter for live width be 10 microns, distance between centers of tracks is 20 microns, and line height is 8 microns, height of projection 8 microns.Assemble nanometer generator output voltage 100 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 3
The present embodiment 3 use silver-colored grid parameter for live width be 20 microns, distance between centers of tracks is 60 microns, and line height is 8 microns, and height of projection 8 microns, other parameter is with embodiment 1.Assemble nanometer generator output voltage 80 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 4
The present embodiment 4 use silver-colored grid parameter for live width be 20 microns, distance between centers of tracks is 100 microns, and line height is 8 microns, and height of projection 8 microns, other parameter is with embodiment 1.Assemble nanometer generator output voltage 60 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 5
The supporting layer thickness that the present embodiment 5 uses is 25 microns, other parameter and assemble nanometer generator performance are suitable with embodiment 1, but nano generator deflection is inadequate, are not easy to test.
Embodiment 6
The supporting layer thickness that the present embodiment 6 uses is 175 microns, and assemble nanometer generator performance is suitable with embodiment 1.
Embodiment 7
With embodiment 1, the mass percent of high molecular polymer and curing agent is 10:1, and at 80 DEG C, dry 40 minutes, hardening time, comparatively embodiment 1 increased, and assemble nanometer generator performance is suitable with embodiment 1.
Embodiment 8
With embodiment 7, the mass percent of high molecular polymer and curing agent is 100:20, and at 80 DEG C, dry 25 minutes, hardening time, comparatively embodiment 7 reduced, and part bubble appears in film between two parties.
Embodiment 9
With embodiment 1, embodiment 9 use silver-colored grid parameter for live width be 10 microns, distance between centers of tracks is 20 microns, and line height is 2 microns, height of projection 2 microns.Assemble nanometer generator output voltage 80 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 10
With embodiment 1, embodiment 10 use silver-colored grid parameter for live width be 10 microns, distance between centers of tracks is 20 microns, and line height is 10 microns, height of projection 10 microns.Assemble nanometer generator performance is suitable with embodiment 1.
Embodiment 11
With embodiment 1, embodiment 11 is peeled off from silver-colored grid after film drying between two parties, and obtaining gross thickness is 50 microns, assemble nanometer generator output voltage 50 volts, output current 8 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 12
With embodiment 1, embodiment 12 is peeled off from silver-colored grid after film drying between two parties, and obtaining gross thickness is 500 microns, assemble nanometer generator output voltage 80 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 13
With embodiment 1, film is at 60 DEG C between two parties for embodiment 13, and dry 60 minutes, assemble nanometer generator performance was suitable with embodiment 1.
Embodiment 14
With embodiment 1, film is at 100 DEG C between two parties for embodiment 14, and dry 20 minutes, the part of film appearance was between two parties peeled phenomenon, assemble nanometer generator output voltage 90 volts, output current 10 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
Embodiment 15
With embodiment 1, embodiment 15 uses polymethyl methacrylate to do thin-film material between two parties.Assemble nanometer generator output voltage 60 volts, output current 4 microamperes, and repeated presses 30,000 ten thousand performances are unattenuated.
The invention provides a kind of with the friction generator after the optimizing structure of micro-structural frictional layer, and the macromolecule frictional layer of micro-structural utilizes dexterously to prepare as the material silver waffle slab of nanometer generating machine electrode.Without the need to the technique of complexity in actual mechanical process, have simple to operate, operating cost is low, and equipment investment less and can the advantage of mass production.
The present invention is not limited to above-described embodiment, and when not deviating from flesh and blood of the present invention, any simple distortion, replacement all should belong to protection scope of the present invention.
Claims (10)
1. a nanometer engine preparation method for film between two parties, is characterized in that, comprise the following steps:
A), on base film prepare metal grill, with absolute ethyl alcohol or acetone cleaning, obtain aperture 10-100 micron, the metal grill template of netting twine height 2-10 micron, netting twine width 10-40 micron;
B, in metal grill template, be coated with the mixture that is made up of high molecular polymer and curing agent of one deck;
C), at 60 ~ 100 DEG C, solidify 20 ~ 60 minutes;
D, stripping; Obtain film between two parties;
Described high molecular polymer is one or more in dimethyl silicone polymer, Kynoar, polymethyl methacrylate, polystyrene, Merlon and PETG;
Described curing agent is silane coupler;
The mass ratio of described high molecular polymer and curing agent is 100:1 ~ 100:20.
2. the preparation method of film between two parties according to claim 1, is characterized in that, described metal grill is prepared by the way of silver halide exposure imaging.
3. the preparation method of film between two parties according to claim 2, is characterized in that, described metal grill contains 50 ~ 100% silver medals.
4. the preparation method of film between two parties according to claim 3, is characterized in that, the shape of described metal grill cross section is circle, square, rectangle, hexagon, triangle.
5. the preparation method of film between two parties according to claim 4, is characterized in that, the mass ratio of high molecular polymer and curing agent is 100:5 ~ 100:10.
6. the preparation method of film between two parties according to claim 5, is characterized in that, described metal grill resistance is 150 ± 50m Ω/.
7. require according to claim the film between two parties that described in 1-6 prepared by method, it is characterized in that, described film between two parties comprises body and bossing, and the gross thickness of film is 50-500 micron between two parties.
8. a nano generator, is characterized in that, described nano generator comprises the obtained film between two parties of method described in claim 1-6 any one.
9. generator according to claim 8, it is characterized in that, described nano generator also comprises metal grid electrode.
10. generator according to claim 8 or claim 9, it is characterized in that, described nano generator sets gradually the first electrode layer 1, between two parties film 2, the second electrode lay 3 and supporting layer 4, and described second electrode is metal grill template.
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| CN201510091301.4A CN104802350A (en) | 2015-03-01 | 2015-03-01 | Preparation method of intermediate film, intermediate film and nano-generator prepared from intermediate film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108233762A (en) * | 2018-03-22 | 2018-06-29 | 大连理工大学 | A kind of flexible wearable friction nanometer power generator of comprehensive multi-mode collecting mechanical energy |
| CN108429482A (en) * | 2017-02-15 | 2018-08-21 | 北京纳米能源与系统研究所 | Friction nanometer power generator, micro-mechanic sensor and sensor-based system |
| CN111133671A (en) * | 2017-07-25 | 2020-05-08 | 剑桥实业有限公司 | Triboelectric generator, method for producing same and components thereof |
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| CN101540371A (en) * | 2009-04-15 | 2009-09-23 | 河北大学 | Flexible polymer solar battery of anode layer of metal grid and preparation method |
| CN102710166A (en) * | 2012-04-13 | 2012-10-03 | 纳米新能源（唐山）有限责任公司 | Friction generator |
| CN103532425A (en) * | 2012-07-05 | 2014-01-22 | 纳米新能源（唐山）有限责任公司 | Nanometer friction generator driven by magnetic field |
| CN104340950A (en) * | 2013-07-24 | 2015-02-11 | 纳米新能源（唐山）有限责任公司 | Preparing method of film having micro-nano structure and frictional electric generator adopting the film |
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Patent Citations (4)
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| CN101540371A (en) * | 2009-04-15 | 2009-09-23 | 河北大学 | Flexible polymer solar battery of anode layer of metal grid and preparation method |
| CN102710166A (en) * | 2012-04-13 | 2012-10-03 | 纳米新能源（唐山）有限责任公司 | Friction generator |
| CN103532425A (en) * | 2012-07-05 | 2014-01-22 | 纳米新能源（唐山）有限责任公司 | Nanometer friction generator driven by magnetic field |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108429482A (en) * | 2017-02-15 | 2018-08-21 | 北京纳米能源与系统研究所 | Friction nanometer power generator, micro-mechanic sensor and sensor-based system |
| CN108429482B (en) * | 2017-02-15 | 2019-11-15 | 北京纳米能源与系统研究所 | Friction nanometer power generator, micro-mechanic sensor and sensor-based system |
| CN111133671A (en) * | 2017-07-25 | 2020-05-08 | 剑桥实业有限公司 | Triboelectric generator, method for producing same and components thereof |
| CN108233762A (en) * | 2018-03-22 | 2018-06-29 | 大连理工大学 | A kind of flexible wearable friction nanometer power generator of comprehensive multi-mode collecting mechanical energy |
| CN108233762B (en) * | 2018-03-22 | 2023-12-22 | 大连理工大学 | Flexible wearable friction nano generator capable of collecting mechanical energy in omnibearing multimode mode |
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Effective date of registration: 20160721 Address after: 071054 Kennan street, Hebei, Baoding, No. 6 Applicant after: Lucky Medical Technology Co Ltd Address before: 071054 Kennan street, Hebei, Baoding, No. 6 Applicant before: China Lucky Group Corporation |
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