CN106301063A - A kind of two-sided wearable friction nanometer power generator and preparation method thereof - Google Patents
A kind of two-sided wearable friction nanometer power generator and preparation method thereof Download PDFInfo
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- CN106301063A CN106301063A CN201610895331.5A CN201610895331A CN106301063A CN 106301063 A CN106301063 A CN 106301063A CN 201610895331 A CN201610895331 A CN 201610895331A CN 106301063 A CN106301063 A CN 106301063A
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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Abstract
The invention provides a kind of two-sided wearable friction nanometer power generator and preparation method thereof, this friction nanometer power generator includes: stack gradually first high molecular polymer thin layer of distribution, friction electrode layer and second high molecular polymer friction film layer, human body is as the second electrode, it is connected with the earth, two-layer friction film is all to be formed by flexible high molecular polymer, and outer surface is all modified with nanostructured；Described flexible macromolecule polymer film layer may be worn on human body, with human body skin phase mutual friction；Described friction electrode layer is the voltage and current output electrode of friction nanometer power generator.Utilize the flexible material of the concavo-convex nanostructured of surface modification as two-layer high molecular polymer thin layer, add minute projections and contact area, produce more charge inducing.The friction nanometer power generator that the present invention provides uses unique both surface friction layer and flexible material, can collect the energy of different directions, it is achieved the output of higher energy.
Description
Technical field
The invention belongs to new energy development and micro-nano structure manufacture field, be specifically related to a kind of two-sided wearable friction and receive
Rice electromotor and preparation method thereof.
Background technology
Along with the fast development of modern science and technology, electronic equipment and system constantly towards miniaturization, portable, multifunction etc.
Direction develops, and portable type electronic product is day by day close with our life, and currently used wearable device has become as masses and disappears
The new trend taken and new fashion.The most real-time to the minitype portable power electronic equipment of these substantial amounts become industry and
Problem demanding prompt solution in Information Technology Development.
Triboelectrification is the most universal a kind of phenomenon in daily life, depends on the electropolar difference of friction of contact material
Not, contact surface surface formed triboelectric charge, produce electrostatic, be a kind of typical changes mechanical energy be the physical phenomenon of electric energy.
2011, king taught research team and just issues in the coupling making full use of triboelectrification and electrostatic induction clear first in the world
Individual friction nanometer power generator, demonstrates surface and modifies the rubbing surface of micro nano structure and can improve generating efficiency.In order to realize
Can collect the friction nanometer power generator of the portable Wearable of human body mechanical energy, Wang Zhonglin professor seminar in 2013 and Chongqing are big
The Zhang Hulin seminar learned have developed single electrode franklinic electricity nano generator based on human skin design the most same time,
It is made up of the polymer friction electrode of single ground connection, when human body skin contacts with polymerization object plane, produces triboelectric charge, once skin
Skin leaves polymer surfaces, and electronics flows to the earth, repeat regular touch and separate can on external circuits output AC
Electric current, it is achieved generating.This unipolar friction nanometer power generator is especially suitable for carrying with, and supplies for portable electric appts
Electricity.But this Wearable friction nanometer power generator only one of which rubbing surface can be modified process, and energy conversion efficiency must
So reduce, and structure fabrication processes is the most single, poor repeatability, causes its application to be severely limited, it would be highly desirable to further
Further investigation.
Summary of the invention
The technical problem to be solved in the present invention is: low for wearable friction nanometer power generator efficiency, processing method is single
Defect, the present invention provides a kind of two-sided wearable friction nanometer power generator and preparation method thereof, by frictional layer by current
One side is promoted to two-sided, collects the energy of more direction, and modifies nanostructured on rubbing surface, improves minute projections
And contact area, export higher voltage and current, it is achieved the high-energy output of wearable friction nanometer power generator.
In order to solve above-mentioned technical problem, present invention provide the technical scheme that a kind of two-sided wearable friction nanometer
Electromotor, this friction nanometer power generator includes: stack gradually first high molecular polymer thin layer of distribution, and rub electrode layer
And second high molecular polymer friction film layer, human body, as the second electrode, is connected with the earth, and two-layer friction film is all
It is to be formed by flexible high molecular polymer, outer surface is all modified with nanostructured；Described flexible macromolecule polymer thin
Film layer may be worn on human body, with human body skin phase mutual friction；Described friction electrode layer be friction nanometer power generator voltage and
Electric current output electrode.
Aforesaid friction nanometer power generator, described high molecular polymer thin film is double-deck, with human contact's friction
Rubbing surface is two plane type.
Aforesaid friction nanometer power generator, described high molecular polymer thin layer two-layer is one or separate type,
Material therefor is same or different；Material employed in it is flexible macromolecule polymer poly dimethyl siloxane
(PDMS), polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), Merlon (PC), UV solidify glue
NOA61 or sulfydryl-alkene (Thiol-ene), thickness is 0.1-2mm.
Aforesaid friction nanometer power generator, described high molecular polymer thin film outer surface is modified nanostructured, nanometer
Physical dimension is 10-500nm, degree of depth 1-30 μm, and wherein nanostructured is nanometer point, nanoneedle, nano-pillar, nano-particle.
Aforesaid friction nanometer power generator, described friction electrode layer is the first electrode, the second electrode be human body skin or
Garment fabric.
Aforesaid friction nanometer power generator, described friction electrode layer selects conductive material, Graphene, electro-conductive glass, gold
Belonging to or alloy, wherein metal is gold, silver, aluminum, nickel, copper, ferrum, titanium, tungsten.
Aforesaid friction nanometer power generator, the thickness of described friction electrode layer is 0.1-10 μm.
The second technical scheme that the present invention provides is, the preparation method of a kind of two-sided wearable friction nanometer power generator should
Method includes:
Step (1) prepares two plane type nanostructured frictional layer
Outer surface on two-layer polymer membrane prepares the structure of nanoscale, and structured one side will not had to connect
Together, the nanostructured frictional layer of two plane type is obtained；
Step (2) preparation friction electrode
Between the frictional layer in two-layer non-structure face, add one layer of conductive layer, collect the charge inducing of two-layer rubbing surface, shape
Become friction electrode；
Step (3) prepares two plane type friction nanometer power generator
By integrated to the two plane type frictional layer in step (1) and step (2) and friction electrode package, stack gradually ground floor and rub
Wipe layer, friction electrode layer and second layer frictional layer, obtain two plane type friction nanometer power generator.
The preparation method of aforesaid friction nanometer power generator, in step (1), for separate type two-layer frictional layer, employing is received
Rice stamping technique prepares nanostructured on two-layer high molecular polymer surface respectively, is then bonded together in non-structure face；Pin
Both surface friction layer to integral type, uses optical exposure technology, dry etch process to combine dual-side imprinting technology one-shot forming double
Face nanostructured.
The preparation method of aforesaid friction nanometer power generator, in step (2), for separate type two-layer frictional layer, uses electricity
A son bundle evaporation coating technique floor height Molecularly Imprinted Polymer back side plating conductive layer wherein is as friction electrode；Two-sided for integral type rubs
Wipe layer, by the centre of conductive material insert material before material curing molding, form one layer of electrode layer, cut off two rubbing surfaces.
The preparation method of aforesaid friction nanometer power generator, in step (3), utilizes heat cure polydimethylsiloxane
Or the sulfydryl-alkene (Thiol-ene) of ultraviolet light polymerization is as adhesives, by integrated to two-layer frictional layer and friction electrode (PDMS)
Encapsulation.
Present invention advantage compared with prior art is:
(1) present invention uses two-sided frictional layer, can collect the energy of different directions, repaiies on frictional layer surface simultaneously
Adorn concavo-convex nanostructured, more preferable with the effect of human body friction, it is achieved that the output of higher energy.
(2) configuration of the present invention is varied, and processing method has a variety of, and motility is high, good process repeatability.
(3) friction nanometer power generator that the present invention provides is flexible, can be fitted in human skin or be worn on human body
On, it is achieved that the purpose powered for portable type electronic product whenever and wherever possible.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of two-sided wearable friction nanometer power generator；
Fig. 2 is the friction nanometer power generator preparation flow figure of double-face nanometer pillar array structure；
Fig. 3 is the preparation flow figure of the friction nanometer power generator of double-face nanometer point array structure；
Fig. 4 is the microphotograph of the nano-pillar array structure prepared.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, below by following specific embodiment,
The present invention is described in further detail.
The present invention is a kind of two-sided wearable friction nanometer power generator and preparation method thereof, uses surface finish nano knot
The flexible macromolecule polymer of structure is as frictional layer, when friction generator and the regular contact separation of human body skin of the present invention
Time, in the external circuit between the friction electrode and the earth of friction generator, form periodic alternating current.This clearly demarcated selection
Harmless flexible high molecular material, can be worn on human body, uses the frictional layer of two plane type simultaneously, can be with collector
The mechanical energy of body more direction, it is achieved the output of electromotor higher energy.
As it is shown in figure 1, the two-sided wearable friction nanometer power generator of a kind of detailed description of the invention of the present invention, including successively
First high molecular polymer frictional layer 1 of stacked distribution, rub electrode layer 2, second layer high molecular polymer frictional layer 3；Two-layer
Nano array structure 4 and lower nano array structure 5 it is modified with respectively on the outer surface of high polymer layer.Described two-layer
The outer surface of high polymer layer contacts friction with human skin, and produces electrostatic charge at friction electrode layer 2；Described rubs
Wipe electrode layer 2 and human body is the electrode of friction nanometer power generator, between friction electrode layer 2 and the earth, form external circuit, output electricity
Pressure and electric current.
In the present invention, ground floor high molecular polymer 1 and the material selected by second layer high molecular polymer 3 must be soft
Property, can be worn on human body and human body is not produced harm and uncomfortable material, meet the material of this condition all at this
In bright protection domain, such as polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polypropylene (PP),
Polyethylene (PE), Merlon (PC), UV solidification glue NOA61 or sulfydryl-alkene (Thiol-ene), thickness is 0.1-2mm, first
Material selected by high molecular polymer frictional layer 1 and second layer high molecular polymer frictional layer 3 can be identical, it is also possible to
It is different.The present invention the preferably first high molecular polymer frictional layer 1 and the material phase of second layer high molecular polymer frictional layer 3
With, preferably macromolecule polymer material is polyethylene terephthalate (PET) or sulfydryl-alkene (Thiol-ene), and thickness is
1mm。
The present invention is modified with on the outer surface of frictional layer nano array structure 4 and lower nano array structure 5 respectively.Its
Middle nano array structure includes the structures such as nanometer point, nanoneedle, nano-pillar, nano-particle, nano-pore.The parameter of nanostructured is i.e.
Width, the degree of depth, cycle, arrangement mode etc., can be adjusted according to concrete use demand, preferably the parameter of nanostructured
For: being shaped as nano-pillar and nanometer point array structure, the size of nano-pillar diameter or nanometer point is 10-500nm, and the degree of depth is 1-
30 μm, are periodically evenly distributed on the face of frictional layer 1 and 3；The preferably cycle of nano-array is 0.1-1 μm.Nano-array
Structure 4 and 5 can be identical, it is also possible to is different.
Friction electrode layer 2 does not has particular provisions to selected material, it is possible to form the material of conductive layer all in the present invention
Protection domain in, such as Graphene, electro-conductive glass, metal or alloy, wherein metal be gold, silver, aluminum, nickel, copper, ferrum, titanium,
Tungsten；Alloy is the alloy of above-mentioned metal.The present invention electrode layer 2 that preferably rubs is silver, and ductility is good, lightweight, can be the most curved
Folding does not ruptures, and thickness is 0.1-10 μm, does not affect the flexible bendable characteristic of friction nanometer power generator.
As in figure 2 it is shown, the following detailed description of the preparation method of above-mentioned two-sided wearable friction nanometer power generator, the method
Comprise the steps:
(1) two plane type nano-pillar array structure frictional layer is prepared
Utilize nano-pore as template, use nanometer embossing to obtain two plane type on two-layer high molecular polymer thin film
Frictional layer.
The template that the present invention can use can be multiaperture pellumina.
The present invention uses the ultraviolet light curing nano stamping technique sacrificing template to prepare nano-pillar array structure, such as, utilize
One piece of a diameter of 200nm, the porous anodic alumina template 21 of the degree of depth 5 μm, template area is 3cm × 3cm, and weight is 2g, profit
It is cleaned processing to its surface with alcoholic solution.Preparation viscosity is 3.5cp, and Young's modulus is the liquid UV light solidification of 1GPa
Sulfydryl-alkene material, utilizes dropper to drip a drop of liquid sulfydryl-alkene material in template, tilts shake template gently, form one layer all
Even thickness is the sulfydryl-alkene material layer 22 of 1mm, and sulfydryl-alkene material also can overcome the surface tension run-in-hole of nano-pore simultaneously
Inside it is filled with completely.Placing and irradiate solidification under ultraviolet light, temperature is 21 DEG C, and light intensity is 40mW/cm2, hardening time is
1min.The method utilizing wet etching dissolves porous alumina formwork, the NaOH aqueous corrosion using concentration to be 10g/mL
Falling template, the speed of corrosion is 6g/h, and the time is 20min, the nano-pillar structure 23 of sulfydryl-alkene material under final residual.Nanometer
The electron scanning micrograph of pillar array structure is as shown in Figure 5.The diameter of nano-pillar structure in the present invention, the degree of depth and
Away from being adjusted according to preparation process condition, the size of such as template, high molecular polymerization physical performance, etching time and temperature
Degree, it is thus achieved that meet the requirement of use condition.
(2) preparation friction electrode
Conductive material is utilized to make friction electrode between two-layer high molecular polymer frictional layer, and between the earth outside formation
Circuit, output voltage and electric current.
The present invention uses the back side one layer of gold of evaporation of electron beam evaporation technique one layer of sulfydryl-alkene nano-pillar thin film wherein
Belong to silver layer, set the operating pressure of plated film as 1.0 × 10-3Pa, temperature is 60～80 DEG C, and power is 8000W, and electronic beam current is
100mA, the speed arranging plated film is 0.1nm/s, and the time is 50min, and the thickness of film layer is 300nm, prepares friction electrode 24.
(3) two plane type friction nanometer power generator is prepared
Two-layer sulfydryl in step (1) and (2)-alkene nano-pillar film bond is got up.
The present invention uses the sulfydryl-alkene material of ultraviolet light polymerization, is uniformly coated with at the back side of a nano-pillar thin film and is covered with
One layer of material layer the thinnest, uses spin coater to carry out rotary coating, and thickness is 1 μm.Nano-pillar structure sheaf by plating silver
Metal covering be fitted on material thin-layer, extrude bubble, be placed under ultraviolet leds lamp irradiation solidification, light intensity is 20mW/cm2,
Time is 1min.Owing to sulfydryl-alkene material has stronger metal adhesion, obtain well-set two plane type friction nanometer and send out
Motor 25.
As it is shown on figure 3, the system of the two-sided wearable friction nanometer power generator the following detailed description of another embodiment
Preparation Method, the method comprises the steps:
(1) two plane type nanometer point array structure frictional layer is prepared
Utilize micron pore array as mask plate, use optical exposure fabrication techniques nanometer point array structure motherboard, then
PlacingJi Shu is utilized to be fabricated to impression block.
The present invention uses optical exposure technology to combine dry etching process to prepare nanometer point array structure impression block, such as
Utilizing one piece of bore is 3 μm, and the cycle is 5 μm, presents the microwell array structure of hexagon or tetragon arrangement as exposed mask
Plate 31.Utilizing the optical exposure technology of i line 34 to expose bore on quartz or glass for the photoresist 32 of substrate 33 is 3 μ
M, height is 2 μm, and the cycle is the nano-pillar array structure 35 of 5 μm.Utilize reactive ion etching machine (RIE) that photoresist is revolved
Turning etching, angle of inclination is 120 °, etching gas sulfur hexafluoride, and flow is 20sccm, and etching power is 150W, and operating pressure is
1.0×10-2Pa, etch period is 30min, it is thus achieved that bore is 2 μm, and height is 1 μm, and the cycle is the nanometer point array structure of 5 μm
Motherboard 36.
The present invention uses placingJi Shu to make impression block, for example with polydimethylsiloxane (PDMS) as template material
Material, mixes 37 by substrate liquid and firming agent with the ratio uniform of 10:1, is cast on nanometer point array structure motherboard, treats that material fills
After point filling, being placed in vacuum drying oven, the vacuum setting vacuum drying oven is 80 DEG C as 0.02Pa, temperature, and heat time heating time is
2h.Exit and take out, the PDMS after solidification is taken off from motherboard gently, it is thus achieved that the structure complementary with nanometer point array structure
38, make the impression block of two PDMS in this way.
The present invention uses soft lithography to make two plane type nanometer point structural friction layer, such as, utilize the impressing of two pieces of PDMS
Template, is stamped on two sides sulfydryl-alkene material layer 311 respectively, and the viscosity of sulfydryl-alkene material is 3.5cp, and Young's modulus is
1GPa, solidification energy density is 20mJ/cm2.After ultraviolet light polymerization, peel off PDMS impression block, it is thus achieved that the nanometer of two plane type
Point array structure 312, the bore of nanometer point is 2 μm, and height is 1 μm, and the cycle is 5 μm.
(2) preparation friction electrode
Use nano silver wire to be embedded between two-layer frictional layer as friction electrode as conductive material, such as, make purple
During outer optic-solidified adhesive NOA61 thin film 39, put open for nano silver wire uniform spreading, then by uniform for the NOA61 of liquid
Drop coating is on nano silver wire film layer, and after ultra-violet curing, nano silver wire is together with NOA61 film bond；NOA61 thin film is turned over
Turning, nano silver wire face is exposed to above, same drop coating NOA61, after ultraviolet light polymerization, is fabricated to the middle nano silver wire that embeds and conducts electricity
The NOA61 thin film of layer 310, thickness is 2mm.
(3) two plane type friction nanometer power generator is prepared
The NOA61 thin film of nano silver wire conductive layer and the processing method knot in step (1) is embedded in the middle of in step (2)
Close, it is thus achieved that the middle two plane type friction nanometer power generator 312 embedding nano silver wire friction electrode layer.
Non-elaborated part of the present invention belongs to the known technology of those skilled in the art.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (11)
1. a two-sided wearable friction nanometer power generator, it is characterised in that: this friction nanometer power generator includes: stack gradually
First high molecular polymer thin layer of distribution, friction electrode layer and second high molecular polymer friction film layer, people
Body, as the second electrode, is connected with the earth, and two-layer friction film is all to be formed, on outer surface by flexible high molecular polymer
All it is modified with nanostructured；Described flexible macromolecule polymer film layer may be worn on human body, mutually rubs with human body skin
Wipe；Described friction electrode layer is the voltage and current output electrode of friction nanometer power generator.
Friction nanometer power generator the most according to claim 1, it is characterised in that: described high molecular polymer thin film is double
Layer, be two plane type with the rubbing surface of human contact's friction.
Friction nanometer power generator the most according to claim 2, it is characterised in that: described high molecular polymer thin layer two
Layer is one or separate type, and material therefor is same or different；Material employed in it is that flexible macromolecule gathers
Compound polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), poly-carbon
Acid esters (PC), UV solidification glue NOA61 or sulfydryl-alkene (Thiol-ene), thickness is 0.1-2mm.
Friction nanometer power generator the most according to claim 2, it is characterised in that: described high molecular polymer thin film appearance
Modifying nanostructured on face, nanostructure size is 10-500nm, degree of depth 1-30 μm, and wherein nanostructured is nanometer point, nanometer
Pin, nano-pillar, nano-particle.
5. according to the friction nanometer power generator described in any one of claim 1-4, it is characterised in that: described friction electrode layer is
First electrode, the second electrode is human body skin or garment fabric.
6. according to the friction nanometer power generator described in any one of claim 1-4, it is characterised in that: described friction electrode layer choosing
With conductive material, Graphene, electro-conductive glass, metal or alloy, wherein metal is gold, silver, aluminum, nickel, copper, ferrum, titanium, tungsten, wherein
Alloy is above-mentioned metal.
7. according to the friction nanometer power generator described in any one of claim 1-4, it is characterised in that: described friction electrode layer
Thickness is 0.1-10 μm.
8. according to the preparation method of the friction nanometer power generator described in any one of claim 1-7, it is characterised in that: the method bag
Include following steps:
Step (1) prepares two plane type nanostructured frictional layer
Outer surface on two-layer polymer membrane prepares the structure of nanoscale, and structured one side will not had to be connected to one
Rise, obtain the nanostructured frictional layer of two plane type；
Step (2) preparation friction electrode
Adding one layer of conductive layer between the frictional layer in two-layer non-structure face, collect the charge inducing of two-layer rubbing surface, formation rubs
Wipe electrode；
Step (3) prepares two plane type friction nanometer power generator
By integrated to the two plane type frictional layer in step (1) and step (2) and friction electrode package, stack gradually ground floor friction
Layer, friction electrode layer and second layer frictional layer, obtain two plane type friction nanometer power generator.
The preparation method of friction nanometer power generator the most according to claim 8, it is characterised in that: in step (1), for dividing
From formula two-layer frictional layer, use nanometer embossing to prepare nanostructured on two-layer high molecular polymer surface respectively, then will
Non-structure face bonds together；For the both surface friction layer of integral type, optical exposure technology, dry etch process is used to combine double
Face stamping technique one-shot forming double-face nanometer structure.
The preparation method of friction nanometer power generator the most according to claim 8, it is characterised in that: in step (2), for
Separate type two-layer frictional layer, uses an electron beam evaporation technique floor height Molecularly Imprinted Polymer back side plating conductive layer wherein as friction
Electrode；For the both surface friction layer of integral type, by the centre of conductive material insert material before material curing molding, form one layer
Electrode layer, cuts off two rubbing surfaces.
The preparation method of 11. friction nanometer power generator according to claim 8, it is characterised in that: in step (3), utilize
Sulfydryl-the alkene (Thiol-ene) of heat cure polydimethylsiloxane (PDMS) or ultraviolet light polymerization is as adhesives, by two-layer
Frictional layer and friction electrode integration packaging.
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| CN111510015A (en) * | 2020-03-23 | 2020-08-07 | 华东师范大学 | Friction nano generator with friction layer double-sided microstructure and preparation method thereof |
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