CN104426416B

CN104426416B - The friction generator of application semiconductor composite

Info

Publication number: CN104426416B
Application number: CN201310389137.6A
Authority: CN
Inventors: 殷亮; 李洁; 王竹; 赵豪
Original assignee: Nano New Energy Tangshan Co Ltd
Current assignee: Nano New Energy Tangshan Co Ltd
Priority date: 2013-08-30
Filing date: 2013-08-30
Publication date: 2016-12-28
Anticipated expiration: 2033-08-30
Also published as: CN104426416A

Abstract

The invention provides the friction generator of application semiconductor composite.This friction generator includes the first electrode layer that stacking is arranged, the first polymer material layer, and the second electrode lay, and wherein the first polymer material layer material therefor is the semiconductor composite of metal doped polymer.Doping metals granule of the present invention, in insulating polymer, reduces the resistivity of polymer so that it is specific insulation level between metal volume resistivity and insulant volume resistivity.Friction generator of the present invention can effectively reduce the work internal resistance of electromotor, can improve the load capacity of friction generator within the specific limits.

Description

The friction generator of application semiconductor composite

Technical field

The present invention relates to triboelectricity field, especially relate to a kind of applied metal doped polymer semiconductor composite Friction generator.

Background technology

At present, energy problem is one of key subjects affecting human progress and sustainable development.Various around new forms of energy Exploitation, the repeatable research utilizing the renewable sources of energy are carried out the most in high gear.

Use collection of energy and the conversion equipment of friction techniques structure, play a crucial role in self-powered nanosystems.And And, owing to it possesses environmental protection, low cost, the characteristic such as self-driven, receive extensive concern.Along with Wang Zhonglin teaches seminar's research and development Piezoelectricity friction electromotor realized since mechanical energy is converted to electric energy, the different structure based on piezoelectricity and franklinic electricity and material Friction generator come out one after another.At present, friction generator can drive small liquid crystal display, low-power light emitting diode And microelectronic device and module etc., but the output performance of electromotor remain restriction its development and application key because of Element.

Summary of the invention

The technical problem to be solved is: overcome the defect of existing friction generator output performance, it is provided that one Plant the friction generator of metal doped polymer semiconductor composite, the load capacity of friction generator can be significantly improved.

Conducting metal particles is added in insulating polymer, it is possible to reduce the resistivity of polymer so that it is volume resistance Rate level between metal volume resistivity and insulant volume resistivity, thus obtain the half of metal doped polymer Conductor composite.Metal doped polymer semiconductor composite had both possessed the functional characteristic such as electric conductivity of metallic particles, Also there is the excellent mechanical performance of polymeric material and machinability.In friction generator, use semiconductor compound material can Effectively to reduce the work internal resistance of electromotor, the load capacity of friction generator can be improved within the specific limits.

But, the difference of character between metallic particles and polymer, the compatibility making both is poor, thus easily causes gold The reunion of metal particles, affects the performance of semiconductor composite.Accordingly, it would be desirable to metallic particles is carried out surface modification so that it is energy Enough stable dispersions are in the polymer matrix.

In order to solve above-mentioned technical problem, the first technical scheme that the present invention provides, a kind of application semiconductor composite Friction generator, the first electrode layer arranged including stacking, the first polymer material layer, and the second electrode lay, wherein first Polymer material layer material therefor is the semiconductor composite of metal doped polymer.

Aforesaid friction generator, in two faces that the first polymer material layer and the second electrode lay are oppositely arranged at least Arranging micro-nano concaveconvex structure on one face, the micro-nano concaveconvex structure that described first polymer material layer surface is arranged is protruding high The micro-nano concaveconvex structure of degree 200nm-100 μm；The micro-nano concaveconvex structure arranged on described the second electrode lay surface is height of projection The micro-nano concaveconvex structure of 200nm-100 μm.

Aforesaid friction generator, the first electrode layer material therefor is indium tin oxide, Graphene, nano silver wire film, gold Belonging to or alloy, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is that aluminum closes Gold, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth close Gold, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy；

The second electrode lay material therefor is metal or alloy, wherein metal can be Au Ag Pt Pd, aluminum, nickel, copper, titanium, Chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy can be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese Alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or Tantalum alloy.

Aforesaid friction generator, described friction generator farther includes the second polymer material layer, this second polymerization Thing material layer is arranged between the first polymer material layer and the second electrode lay.

In two faces that aforesaid friction generator, the first polymer material layer and the second polymer material layer are oppositely arranged At least one face on micro-nano concaveconvex structure, described first polymer material layer and/or the second polymer material layer surface are set The micro-nano concaveconvex structure that micro-nano concaveconvex structure is height of projection 200nm-100 μm of upper setting.

Aforesaid friction generator, described second polymer material layer material therefor is the quasiconductor of metal doped polymer Composite.

Aforesaid friction generator, described second polymer material layer material therefor is Kapton, aniline formaldehyde Resin film, polyformaldehyde thin film, ethyl cellulose film, polyamide film, melamino-formaldehyde thin film, Polyethylene Glycol succinic acid Ester film, cellulose membrane, cellulose acetate film, 10PE27 thin film, polydiallyl phthalate Thin film, cellulose sponge thin film, renewable sponge thin film, elastic polyurethane body thin film, styrene-acrylonitrile copolymer copolymer film, styrene Butadiene copolymer thin film, staple fibre thin film, polymethyl methacrylate film, polyvinyl alcohol film, polyisobutylene thin film, Pet film, polyvinyl butyral film, formaldehyde-phenol condensation polymer thin film, neoprene thin film, Any in butadiene-propylene copolymer thin film, natural rubber films, polyacrylonitrile thin film, acrylonitrile vinyl chloride copolymer thin film A kind of.

Aforesaid friction generator, described friction generator farther includes intervening electrode layer, and described intervening electrode layer sets Put between the first polymer material layer and the second polymer material layer.

Aforesaid friction generator, described intervening electrode layer is metal, metal-oxide, alloy-layer, or patterned metal Line-high polymer layer stack, wherein metal be Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or Vanadium；Alloy is aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, stannum conjunction Gold, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy, metal-oxide is indium stannum Oxide.

Patterned metal line-high polymer layer stack of the present invention is logical on a side surface of high polymer layer Cross hot pressing, spin coating, blade coating or screen-printed metal, metal dust or metal paste, form patterned metal line, thus prepare The duplexer obtained.Metal material therefor is metal or alloy, wherein, metal be Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, Selenium, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel Alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy. Metal paste of the present invention includes binding agent, metal dust, diluent etc..Binding agent and diluent are makes the normal of metal paste Rule composition.Here be graphically can turn on graphical, such as well shape structure, diamond shaped structure, Z-shaped structure or interdigital Structure.

In two faces that aforesaid friction generator, the first polymer material layer and intervening electrode layer are oppositely arranged at least On one face, and/or set at least one face in two face being oppositely arranged of the second polymer material layer and intervening electrode layer Putting micro-nano concaveconvex structure, described micro-nano concaveconvex structure is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

Aforesaid friction generator, the first electrode layer and the second electrode lay material therefor are indium tin oxide, Graphene, silver Nano wire film, metal or alloy, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium； Alloy be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, Cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.

Aforesaid friction generator, in parts by weight, described semiconductor composite includes metallic particles 1-50 part, and poly- Polymer substrates material 30-99 part.

Aforesaid friction generator, described semiconductor composite includes metallic particles 1-10 part, and polymeric substrates material Material 90-99 part.

Aforesaid friction generator, described polymeric base material is polydimethylsiloxane, Kynoar, poly-methyl Acrylic acid methyl ester. or polrvinyl chloride.

Aforesaid friction generator, described metallic particles is at least one in silver, copper, gold, aluminum, tungsten, nickel, ferrum, its body Long-pending particle diameter is in 1-100 μm.

Aforesaid friction generator, described metallic particles is through modifier surface modified metallic particles, metallic particles It is 1-50:1 with the weight ratio of modifying agent.

Aforesaid friction generator, described metallic particles is 1-30:1 with the weight ratio of modifying agent.

Aforesaid friction generator, described modifying agent be polyvinylpyrrolidone, cetyl trimethylammonium bromide, double ten Eight alkyl dimethyl ammonium chloride, sodium laurate, enuatrol, sodium lauryl sulphate, γ-chloropropyl trichloro-silane, γ-chloropropyl Trimethoxy silane, gamma-chloropropylmethyldimethoxysilane, VTES, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, β-(3,4 epoxycyclohexyl) ethyl trimethoxy silane, γ-shrink Glycerol ether propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxy Silane, γ-ureidopropyltriethoxysilane, γ-(3,2 glycidoxy) MTMS, γ-mercapto propyl group three second TMOS, γ-(ethylenediamine base) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, double-[3-(triethoxy) Silicon propyl group tetrasulfide, diethylenetriamine base propyl trimethoxy silicane, γ-ethylenediamine ethyl triethoxy silicane alkane, Α-(second two Amido) MTES, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, double (3-triethoxy Silylpropyl) four nitric sulfids, Cyclohexyl Methyl Dimethoxysilane, tetra-n-butyl titanate, tetraisopropoxy titanium, 2-second Base-1-hexanol titanium, metatitanic acid four n-propyl, poly(tributoxy titanium), isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) metatitanic acid Ester, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isopropyl three oleic acid acyloxy titanate esters, isopropyl three (dodecane Base benzenesulfonyl) titanate esters, three stearic acid isopropyl titanates, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (two Octyl group pyrophosphoric acid acyloxy) ethylene titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, double (acetylacetone,2,4-pentanedione Base) (diisopropyl) titanate esters, double (levulinic ketone group) (isobutoxy isopropoxy) titanate esters, double (levulinic ketone group) (second Epoxide isopropoxy) titanate esters, two (triethanolamine) metatitanic acid diisopropyl ester, 2,2 ', 2 "-nitrilo triethyl group titanate esters, double (acetyl Ethyl acetate) at least one in metatitanic acid diisobutyl ester.

Aforesaid friction generator, described modifying agent is sodium lauryl sulphate.

The second technical scheme that the present invention provides, a kind of friction generator, the first electrode layer arranged including stacking, first Polymer material layer, between two parties thin layer, the second polymer material layer and the second electrode lay, wherein, the first polymer material layer and At least one of which in thin layer between two parties, and/or the second polymer material layer and at least one of which material therefor in thin layer between two parties It it is the semiconductor composite of metal doped polymer.

Aforesaid friction generator, in parts by weight, described semiconductor composite includes metallic particles 1-10 part, and poly- Polymer substrates material 90-99 part.

Aforesaid friction generator, in two faces that the first polymer material layer and between two parties thin layer are oppositely arranged at least Micro-nano concaveconvex structure is set on one face, and/or in the second polymer material layer and thin layer is oppositely arranged between two parties two faces At least one face on micro-nano concaveconvex structure is set；

Arrange on described first polymer material layer, and/or thin layer between two parties, and/or the second polymer material layer surface The micro-nano concaveconvex structure that micro-nano concaveconvex structure is height of projection 200nm-100 μm.

Aforesaid friction generator, when the first polymer material layer, or thin layer between two parties, or the second polymer material layer is not Use semiconductor composite time, its material therefor selected from Kapton, aniline-formaldehyde resin thin film, polyformaldehyde thin film, Ethyl cellulose film, polyamide film, melamino-formaldehyde thin film, Polyethylene Glycol succinate thin film, cellulose membrane, fibre Dimension element acetate films, 10PE27 thin film, polydiallyl phthalate thin film, cellulose sponge thin film, Renewable sponge thin film, elastic polyurethane body thin film, styrene-acrylonitrile copolymer copolymer film, styrene-butadiene-copolymer thin film, people Make fiber membrane, polymethyl methacrylate film, polyvinyl alcohol film, polyisobutylene thin film, polyethylene terephthalate Ester film, polyvinyl butyral film, formaldehyde-phenol condensation polymer thin film, neoprene thin film, butadiene-propylene copolymer are thin Any one in film, natural rubber films, polyacrylonitrile thin film, acrylonitrile vinyl chloride copolymer thin film.

Doping metals granule of the present invention, in insulating polymer, reduces the resistivity of polymer so that it is specific insulation is situated between Level between metal volume resistivity and insulant volume resistivity.The semiconductor composite of metal doped polymer Both possessed the functional characteristic such as electric conductivity of metallic particles, it may have mechanical performance that polymeric material is excellent and machinability. This semiconductor compound material is used can effectively to reduce the work internal resistance of electromotor, within the specific limits in friction generator The load capacity of friction generator can be improved.

Accompanying drawing explanation

Fig. 1 is the perspective view of a kind of detailed description of the invention of friction generator of the present invention.

Fig. 2 is the cross-sectional view of Fig. 1 friction generator of the present invention.

Fig. 3 is the perspective view of friction generator another kind detailed description of the invention of the present invention.

Fig. 4 is the cross-sectional view of Fig. 3 friction generator of the present invention.

Fig. 5 is the perspective view of friction generator another kind detailed description of the invention of the present invention.

Fig. 6 is the perspective view of Fig. 5 friction generator of the present invention.

Fig. 7 is the perspective view of friction generator another kind detailed description of the invention of the present invention.

Fig. 8 is the perspective view of Fig. 7 friction generator of the present invention.

Fig. 9 is the open circuit electricity of the friction generator using Cu doped polymer semiconductor composite to be polymer material layer Pressure output valve.

Figure 10 is the 1M Ω of the friction generator using Cu doped polymer semiconductor composite to be polymer material layer Load voltage output valve.

Figure 11 is the open-circuit voltage output valve of the friction generator of conventional polymeric materials layer.

Figure 12 is the 1M Ω load voltage output valve of the friction generator of conventional polymeric materials layer.

Detailed description of the invention

For being fully understood by the purpose of the present invention, feature and effect, by following specific embodiment, the present invention is done in detail Describe in detail bright.

The invention provides the semiconductor composite of a kind of metal doped polymer, in parts by weight, metallic particles 1- 50 parts, and polymeric base material 30-99 part.Preferably metallic particles 1-10 part, and polymeric base material 90-99 part.

Polymeric base material used by the present invention is polydimethylsiloxane, Kynoar, polymethyl methacrylate Or polrvinyl chloride.Above-mentioned material is dissolved in dimethyl acetylamide (DMA), liquid solution can be formed.Polydimethylsiloxane is originally Body is liquid, it is not necessary to be dissolved in dimethyl acetylamide (DMA).

Metallic particles used by the present invention is at least one in silver, copper, gold, aluminum, tungsten, nickel, ferrum, and its particle volume diameter is at 1- 100μm.Preferably, described metallic particles is the weight through modifier surface modified metallic particles, metallic particles and modifying agent Amount ratio is 1-50:1, it is preferred that described metallic particles is 1-30:1 with the weight ratio of modifying agent.

Above-mentioned modifying agent can be polyvinylpyrrolidone, cetyl trimethylammonium bromide, double octadecyldimethyl Ammonium chloride, sodium laurate, enuatrol, sodium lauryl sulphate, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silicon Alkane, gamma-chloropropylmethyldimethoxysilane, VTES, vinyltrimethoxy silane, γ-(methyl-prop Alkene acyloxy) propyl trimethoxy silicane, β-(3,4 epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidyl ether third Base trimethoxy silane, γ-mercaptopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-urea Base propyl-triethoxysilicane, γ-(3,2 glycidoxy) MTMS, gamma-mercaptopropyltriethoxysilane, γ-(ethylenediamine base) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, double-[3-(triethoxy) silicon propyl group four Sulfide, diethylenetriamine base propyl trimethoxy silicane, γ-ethylenediamine ethyl triethoxy silicane alkane, Α-(ethylenediamine base) methyl Triethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, double (3-triethoxysilyl Propyl group) four nitric sulfids, Cyclohexyl Methyl Dimethoxysilane, tetra-n-butyl titanate, tetraisopropoxy titanium, 2-ethyl-1-hexanol Titanium, metatitanic acid four n-propyl, poly(tributoxy titanium), isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl Three (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three oleic acid acyloxy titanate esters, isopropyl three (dodecyl benzene sulfonyl Base) titanate esters, three stearic acid isopropyl titanates, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (dioctyl Jiao's phosphorus Acid acyloxy) ethylene titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, double (levulinic ketone groups) (two is different Propyl group) titanate esters, double (levulinic ketone group) (isobutoxy isopropoxy) titanate esters, double (levulinic ketone group) (ethyoxyl isopropyl Epoxide) titanate esters, two (triethanolamine) metatitanic acid diisopropyl ester, 2,2 ', 2 "-nitrilo triethyl group titanate esters, double (acetoacetic acid second Ester) at least one in metatitanic acid diisobutyl ester.Preferably modifying agent is sodium lauryl sulphate

Preparation method the following detailed description of the most above-mentioned semiconductor composite.The method includes: selectivity step (1) Being modified metallic particles processing, concrete employing modifier carries out surface process to metallic particles, obtains through modifying agent The metallic particles of surface modification.Surface treatment method used by the present invention is Conventional metal particles surface treatment method.

(2) polymeric base material liquid solution is prepared.Concrete, by Kynoar, polymethyl methacrylate or Polrvinyl chloride is dissolved in dimethyl acetylamide (DMA) and forms liquid solution.Polydimethylsiloxane inherently liquid, Ke Yizhi Scoop out for second step.

(3) metallic particles is joined step (2) gained liquid solution mix homogeneously.When polymer uses poly dimethyl silicon During oxygen alkane, needing to use polydimethylsiloxane and firming agent (vulcanizing agent, usual ratio is 10:1), firming agent used is commercially available Conventional solidified dose, such as DOW CORNING 184.

(4) by step (3) gained liquid coating film, drying, obtain at least one side surface and micro-nano concaveconvex structure or two is set Individual side surface is respectively provided with the thin film of micro-nano concaveconvex structure.

The present invention uses the methods such as conventional screen printing, coating, spin coating to prepare in silicon template to have the thin of concaveconvex structure Film.The present invention uses churned mechanically mode (ball milling, magnetic agitation, puddler stir) by material mix homogeneously.

Semiconductor composite of the present invention is applied in friction generator.The following detailed description of application semiconductor composite The structure of friction generator.

It it is the friction generator 1 of a kind of detailed description of the invention of the present invention shown in Fig. 1 and Fig. 2.This friction generator 1 includes layer Folded the first electrode layer 11 arranged, the first polymer material layer 12, and the second electrode lay 13.Wherein, the first polymer material layer 12 material therefors are the semiconductor composite layers of above-mentioned metal doped polymer, and its thickness is 100 μm-500 μm.

Arrange at least one face in two faces that first polymer material layer 12 and the second electrode lay 13 are oppositely arranged Micro-nano concaveconvex structure 14(Fig. 2 only illustrates the micro-nano concaveconvex structure on the first polymer material layer 12), described first polymeric material The micro-nano concaveconvex structure that micro-nano concaveconvex structure is height of projection 200nm-100 μm arranged on bed of material surface；Described second electrode The micro-nano concaveconvex structure that micro-nano concaveconvex structure is height of projection 200nm-100 μm arranged on layer surface.

In this embodiment, the first electrode layer 11 does not has particular provisions to material therefor, it is possible to form the material of conductive layer All within protection scope of the present invention, e.g. indium tin oxide, Graphene, nano silver wire film, metal or alloy, Qi Zhongjin Genus is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy be aluminium alloy, titanium alloy, magnesium alloy, Beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, Tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.

In this embodiment, the second electrode lay 13 material therefor can be metal or alloy, wherein metal can be gold, Silver, platinum, palladium, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy can be aluminium alloy, titanium alloy, magnesium alloy, beryllium Alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten Alloy, molybdenum alloy, niobium alloy or tantalum alloy.The thickness of the second electrode lay 13 preferably 100 μm-500 μm, more preferably 200 μm.

The first polymerization when each layer of the friction generator of this embodiment of the present invention is bent downwardly, in friction generator Thing material layer 12 produces electrostatic charge with the phase mutual friction of the second electrode lay 13 surface, and the generation of electrostatic charge can make the first polymeric material Electric capacity between layer 12 and the second electrode lay 13 changes, thus causes the first polymer material layer 12 and the second electrode lay 13 Between electric potential difference occurs.Due to the existence of electric potential difference, free electron between the first polymer material layer 12 and the second electrode lay 13 To be flowed to, by the side that electromotive force is low, the side that electromotive force is high by external circuit, thus in external circuit, form electric current.When the present invention's When each layer of friction generator returns to original state, be at this moment formed at the first polymer material layer 12 and the second electrode lay 13 it Between built-in potential disappear, will again produce reversely between the most Balanced first polymer material layer 12 and the second electrode lay 13 Electric potential difference, then free electron forms reverse current by external circuit.By repeatedly rubbing and recovering, it is possible in external circuit Form periodic ac signal.In this embodiment of the present invention, use the semiconductor composite of metal doped polymer As the first polymer material layer 12 so that it is specific insulation between metal volume resistivity and insulant volume resistivity it Between level, thus can effectively reduce the work internal resistance of electromotor, the negative of friction generator can be improved within the specific limits Loading capability.

It it is the friction generator 2 of another kind detailed description of the invention of the present invention shown in Fig. 3 and Fig. 4.This friction generator 2 includes The first electrode layer 21 that stacking is arranged, the first polymer material layer 22, the second polymer material layer 23 and the second electrode lay 24, its In, at least one of which material therefor in the first polymer material layer 22 and the second polymer material layer 23 is above-mentioned metal-doped The semiconductor composite layer of polymer, its thickness is 100 μm-500 μm.

At least one face in two faces that first polymer material layer 22 and the second polymer material layer 23 are oppositely arranged On micro-nano concaveconvex structure 25(Fig. 4 is set the micro-nano concaveconvex structure on the first polymer material layer 22 is only shown), this micro-nano is concavo-convex Structure is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

In this embodiment, the first electrode layer 21 and the second electrode lay 24 do not have particular provisions to material therefor, it is possible to Formed conductive layer material all within protection scope of the present invention, e.g. indium tin oxide, Graphene, nano silver wire film, Metal or alloy, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is that aluminum closes Gold, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth close Gold, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.

At least one of which material therefor in first polymer material layer 22 and the second polymer material layer 23 is above-mentioned partly to lead Composite material layer.When the first polymer material layer 22 or the second polymer material layer 23 do not use semiconductor composite layer Time, its material therefor is selected from Kapton, aniline-formaldehyde resin thin film, polyformaldehyde thin film, ethyl cellulose film, polyamides Amine thin film, melamino-formaldehyde thin film, Polyethylene Glycol succinate thin film, cellulose membrane, cellulose acetate film, poly-oneself Naphthalate thin film, polydiallyl phthalate thin film, cellulose sponge thin film, renewable sponge thin film, polyurethane Elastomer thin film, styrene-acrylonitrile copolymer copolymer film, styrene-butadiene-copolymer thin film, staple fibre thin film, poly-methyl-prop E pioic acid methyl ester thin film, polyvinyl alcohol film, polyisobutylene thin film, pet film, polyvinyl alcohol contracting fourth Aldehyde thin film, formaldehyde-phenol condensation polymer thin film, neoprene thin film, butadiene-propylene copolymer thin film, natural rubber films, poly-third Any one in alkene nitrile thin film, acrylonitrile vinyl chloride copolymer thin film.Now, the first polymer material layer 22 or the second polymerization Thing material layer 23 thickness is 100 μm-500 μm.

The first polymerization when each layer of the friction generator of this embodiment of the present invention is bent downwardly, in friction generator Thing material layer 22 produces electrostatic charge with the second polymer material layer 23 surface phase mutual friction, and the generation of electrostatic charge can make the first polymerization Electric capacity between thing material layer 22 and the second polymer material layer 23 changes, thus causes the first electrode layer 21 and the second electricity Between pole layer 24, electric potential difference occurs.Due to the existence of electric potential difference, free electron between the first electrode layer 21 and the second electrode lay 24 To be flowed to, by the side that electromotive force is low, the side that electromotive force is high by external circuit, thus in external circuit, form electric current.When the present invention's When each layer of friction generator returns to original state, be at this moment formed between the first electrode layer 21 and the second electrode lay 24 is interior Electromotive force disappears, and will again produce reverse electric potential difference, then between the most Balanced first electrode layer 21 and the second electrode lay 24 Free electron forms reverse current by external circuit.By repeatedly rubbing and recovering, it is possible to formed periodically in external circuit Ac signal.In this embodiment of the present invention, the semiconductor composite of metal doped polymer is used to gather as first Laminate material layer 22 and/or the second polymer material layer 23 so that it is specific insulation is between metal volume resistivity and insulation material Level between material specific insulation, thus can effectively reduce the work internal resistance of electromotor, can improve within the specific limits The load capacity of friction generator.

It it is the friction generator 3 of another detailed description of the invention of the present invention shown in Fig. 5 and Fig. 6.This friction generator 3 includes First electrode layer 31, the first polymer material layer 32, between two parties thin layer 33, the second polymer material layer 34 and the second electrode lay 35, wherein, at least one of which in the first polymer material layer 32 and between two parties thin layer 33, and/or the second polymer material layer 34 At least one of which material therefor in thin layer 33 is the semiconductor composite layer of above-mentioned metal doped polymer between two parties, its Thickness is 100 μm-500 μm.

Arrange at least one face in two faces that first polymer material layer 32 and between two parties thin layer 33 are oppositely arranged In micro-nano concaveconvex structure (not shown), and/or the second polymer material layer 34 and thin layer 33 is oppositely arranged between two parties two faces At least one face on micro-nano concaveconvex structure (not shown) is set；

When being provided with micro-nano on the first polymer material layer 32, between two parties thin layer 33, the second polymer material layer 34 surface During concaveconvex structure, this micro-nano concaveconvex structure is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

In this embodiment, the first electrode layer 31 and the second electrode lay 35 do not have particular provisions to material therefor, it is possible to Formed conductive layer material all within protection scope of the present invention, e.g. indium tin oxide, Graphene, nano silver wire film, Metal or alloy, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is that aluminum closes Gold, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth close Gold, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.

At least one of which in first polymer material layer 32 and between two parties thin layer 33, and/or the second polymer material layer 34 At least one of which material therefor in thin layer 33 is semiconductor composite layer between two parties.When the first polymer material layer 32, or Thin layer 33 between two parties, or when the second polymer material layer 34 does not use semiconductor composite layer, its material therefor is selected from polyamides Imines thin film, aniline-formaldehyde resin thin film, polyformaldehyde thin film, ethyl cellulose film, polyamide film, melamino-formaldehyde are thin Film, Polyethylene Glycol succinate thin film, cellulose membrane, cellulose acetate film, 10PE27 thin film, poly-neighbour Dially phthalate thin film, cellulose sponge thin film, renewable sponge thin film, elastic polyurethane body thin film, styrene-acrylonitrile copolymer Copolymer film, styrene-butadiene-copolymer thin film, staple fibre thin film, polymethyl methacrylate film, polyvinyl alcohol Thin film, polyisobutylene thin film, pet film, polyvinyl butyral film, formaldehyde-phenol condensation polymer Thin film, neoprene thin film, butadiene-propylene copolymer thin film, natural rubber films, polyacrylonitrile thin film, acrylonitrile vinyl chloride Any one in copolymer film.Now, the first polymer material layer 32, or thin layer 33 between two parties, or the second polymeric material The bed of material 34 thickness is 100 μm-500 μm.

The first polymerization when each layer of the friction generator of this embodiment of the present invention is bent downwardly, in friction generator Thing material layer 32 and thin layer 33 surface between two parties, and/or the second polymer material layer 34 mutually rubs with thin layer 33 surface between two parties Wiping and produce electrostatic charge, the generation of electrostatic charge can make electric potential difference occur between the first electrode layer 31 and the second electrode lay 35.Due to The existence of electric potential difference between one electrode layer 31 and the second electrode lay 35, free electron by by external circuit by the low effluent of electromotive force To the side that electromotive force is high, thus in external circuit, form electric current.When each layer of the friction generator of the present invention returns to original shape During state, the built-in potential being at this moment formed between the first electrode layer 31 and the second electrode lay 35 disappears, the most Balanced first electricity To again produce reverse electric potential difference between pole layer 31 and the second electrode lay 35, then free electron forms reverse electricity by external circuit Stream.By repeatedly rubbing and recovering, it is possible to form periodic ac signal in external circuit.This embodiment of the present invention In, the semiconductor composite of employing metal doped polymer is as the first polymer material layer 32, and/or thin layer between two parties 33, and/or the second polymer material layer 34 so that it is specific insulation is between metal volume resistivity and insulant volume resistance Level between rate, thus can effectively reduce the work internal resistance of electromotor, friction generator can be improved within the specific limits Load capacity.

It it is the friction generator 4 of another detailed description of the invention of the present invention shown in Fig. 7 and 8.This friction generator 4 includes One electrode layer 41, the first polymer material layer 42, intervening electrode layer 43, the second polymer material layer 44 and the second electrode lay 45, Wherein, the metal that at least one of which material therefor in the first polymer material layer 42 and the second polymer material layer 44 is above-mentioned is mixed The semiconductor composite layer of heteropolymer, its thickness is 100 μm-500 μm.

On at least one face in two faces that first polymer material layer 41 and intervening electrode layer 43 are oppositely arranged, and/ Or it is recessed to arrange micro-nano at least one face that second in two faces being oppositely arranged of polymer material layer 44 and intervening electrode layer 43 Male structure (not shown), described micro-nano concaveconvex structure is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

In this embodiment, the first electrode layer 41 and the second electrode lay 45 do not have particular provisions to material therefor, it is possible to Formed conductive layer material all within protection scope of the present invention, e.g. indium tin oxide, Graphene, nano silver wire film, Metal or alloy, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is that aluminum closes Gold, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth close Gold, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.

Described intervening electrode layer 43 is metal, metal-oxide, alloy-layer, or patterned metal line-high molecular polymer Duplexer, wherein metal is Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy be aluminium alloy, Titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, Indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy, metal-oxide is indium tin oxide.

At least one of which material therefor in first polymer material layer 42 and the second polymer material layer 44 is above-mentioned partly to lead Composite material layer.When the first polymer material layer 42 or the second polymer material layer 44 do not use semiconductor composite layer Time, its material therefor is selected from Kapton, aniline-formaldehyde resin thin film, polyformaldehyde thin film, ethyl cellulose film, polyamides Amine thin film, melamino-formaldehyde thin film, Polyethylene Glycol succinate thin film, cellulose membrane, cellulose acetate film, poly-oneself Naphthalate thin film, polydiallyl phthalate thin film, cellulose sponge thin film, renewable sponge thin film, polyurethane Elastomer thin film, styrene-acrylonitrile copolymer copolymer film, styrene-butadiene-copolymer thin film, staple fibre thin film, poly-methyl-prop E pioic acid methyl ester thin film, polyvinyl alcohol film, polyisobutylene thin film, pet film, polyvinyl alcohol contracting fourth Aldehyde thin film, formaldehyde-phenol condensation polymer thin film, neoprene thin film, butadiene-propylene copolymer thin film, natural rubber films, poly-third Any one in alkene nitrile thin film, acrylonitrile vinyl chloride copolymer thin film.Now, the first polymer material layer 42 or the second polymerization Thing material layer 44 thickness is 100 μm-500 μm.

The first polymerization when each layer of the friction generator of this embodiment of the present invention is bent downwardly, in friction generator Thing material layer the 42, second polymer material layer 44 produces electrostatic charge with the phase mutual friction of intervening electrode layer 43 surface respectively, thus leads Cause between the first electrode layer 41 and intervening electrode layer 43, and between intervening electrode layer 43 and the second electrode lay 45, electromotive force occurs Difference.Due between the first electrode layer 41 and intervening electrode layer 43, and electromotive force between intervening electrode layer 43 and the second electrode lay 45 The existence of difference, free electron will be flowed to, by the side that electromotive force is low, the side that electromotive force is high by external circuit, thus shape in external circuit Become electric current.When each layer of the friction generator of the present invention returns to original state, at this moment it is formed at the first electrode layer 41 and occupies Between between electrode layer 43, and the built-in potential between intervening electrode layer 43 and the second electrode lay 45 disappears, the most Balanced the Between one electrode layer 41 and intervening electrode layer 43, and will again produce between intervening electrode layer 43 and the second electrode lay 45 reversely Electric potential difference, then free electron forms reverse current by external circuit.By repeatedly rubbing and recovering, it is possible in external circuit Form periodic ac signal.In this embodiment of the present invention, use the semiconductor composite of metal doped polymer As the first polymer material layer 42 and/or the second polymer material layer 44 so that it is specific insulation is between metal volume resistance Level between rate and insulant volume resistivity, thus can effectively reduce the work internal resistance of electromotor, in certain limit The interior load capacity that can improve friction generator.

Illustrate the enforcement of the method for the present invention below by specific embodiment, skilled artisan would appreciate that It is that this is understood not to the restriction to scope of the invention as claimed.

In embodiment raw materials used as follows:

Table 1

Producer, model

Polydimethylsiloxane	DOW CORNING
		Kynoar	Zhuzhou day Feng Huaxue plastic cement company limited
Polymethyl methacrylate	Qimei Industry Co., Ltd.
		Polrvinyl chloride	The municipal new plastic material company limited in Dongguan
Sodium lauryl sulphate	Tianjin Kai Tong chemical reagent company limited
		γ-chloropropyl trichloro-silane	Mountain of papers boat profit chemical plant, Jishui
Cetyl trimethylammonium bromide	The good Chemical Co., Ltd. of upper maritime affairs
		Tetra-n-butyl titanate	A upper marine Chemical Co., Ltd.

Embodiment 1

Friction generator a size of 3cm × 3cm, gross thickness is about 500 μm.This friction generator 1 includes that stacking is arranged The first electrode layer 11, the first polymer material layer 12, and the second electrode lay 13.Metal used by first polymer material layer 12 is mixed The semiconductor composite of heteropolymer.Preparation method the following detailed description of this friction generator.

1. the preparation of semiconductor composite

Use 7.5g sodium lauryl sulphate that 25g Argent grain (average volume particle diameter 50 μm) is carried out surface process, obtain Through modifier surface modified metallic particles.By this through modifier surface modified metallic particles 5g, firming agent (DOW CORNING 184) join in 95g polydimethylsiloxane (DOW CORNING), obtain mixed slurry, wherein polydimethylsiloxane and firming agent Mass ratio be 10:1.Described slurry is uniformly coated to silicon template surface, after Vacuum Degassing Process, uses and rotate painting Unnecessary slurry is removed by the mode covered, and forms one layer of thin polydimethylsiloxane liquid film.By whole template at 85 DEG C After environment solidifies 1 hour, PDMS membrane is peeled off from silicon template, makes side surface configuration height of projection Semiconductor composite thin film (thickness is 150um) for the micro-nano concaveconvex structure of 500nm.

2. the preparation of friction generator

Using above-mentioned semiconductor composite thin film as the first polymer material layer 12, it is not provided with micro-nano concaveconvex structure Surface on plate thickness 100nm aluminum thin film, this aluminum thin film is the first electrode layer 11.

Use the Copper Foil of thickness 100 μm as the second electrode lay 13.It is provided with wiener according to the first polymer material layer 12 The second electrode lay 13, towards the second electrode lay 13, is stacked on the first polymer material layer 12, obtains by the surface of concaveconvex structure Friction generator 1#.The edge of this friction generator seals with common adhesive plaster.

This friction generator is at I-V(current-voltage) measurement in show typical open circuit feature.Make under 1M Ω load (friction generator works for the bending of friction generator generating period and release, the open-circuit voltage of friction generator and work internal resistance Internal resistance can obtain by the way of triboelectricity resistance under duty by directly measuring) it is respectively 150V and 75M Ω.

Embodiment 2

1. the preparation of semiconductor composite

Use 7.5g sodium lauryl sulphate that 25g alumina particles (average volume particle diameter 50 μm) is carried out surface process, obtain Through modifier surface modified metallic particles.This is joined polyvinylidene fluoride through modifier surface modified metallic particles 5g In the dimethylacetamide solution of alkene (95g), obtain mixed slurry.Described slurry is uniformly coated to silicon template surface, warp After crossing Vacuum Degassing Process, use the mode of rotary coating to be removed by unnecessary slurry, form one layer of thin Kynoar liquid Body film.After whole template is solidified 1 hour in the environment of 85 DEG C, polyvinylidene fluoride film is peeled off from silicon template, makes Side surface configuration height of projection is the semiconductor composite thin film (thickness is 150um) of the micro-nano concaveconvex structure of 500nm.

2. the preparation of friction generator

This friction generator is at I-V(current-voltage) measurement in show typical open circuit feature.Make under 1M Ω load (friction generator works for the bending of friction generator generating period and release, the open-circuit voltage of friction generator and work internal resistance Internal resistance can obtain by the way of triboelectricity resistance under duty by directly measuring) it is respectively 90V and 95M Ω.

Embodiment 3-4

Embodiment 3-4 is essentially identical with the preparation method of embodiment 2, and difference is as shown in table 2.

Table 2

Friction generator 3# and the bending of 4# generating period and release is made, the open circuit electricity of 3# friction generator under 1M Ω load Pressure and work internal resistance are respectively 100V and 70M Ω.The open-circuit voltage of 4# friction generator and work internal resistance are respectively 90V and 90M Ω。

Embodiment 5-8

Embodiment 5-8 is essentially identical with the preparation method of embodiment 1, and difference is as shown in table 3.

Table 3

Bending and the release of friction generator 5#-8# generating period is made, the open circuit electricity of 5# friction generator under 1M Ω load Pressure and work internal resistance are respectively 115V and 85M Ω.The open-circuit voltage of 6# friction generator and work internal resistance are respectively 120V and 80M Ω.The open-circuit voltage of 7# friction generator and work internal resistance are respectively 135V and 80M Ω.The open-circuit voltage of 8# friction generator and Work internal resistance is respectively 130V and 85M Ω.

Embodiment 9

1. the preparation of semiconductor composite

Use 50g sodium lauryl sulphate 50g Argent grain (average volume particle diameter 50 μm) is carried out surface process, obtain through Cross modifier surface modified metallic particles.By this through modifier surface modified metallic particles 1g, firming agent (DOW CORNING 184) join in 99g polydimethylsiloxane (DOW CORNING), obtain mixed slurry, wherein polydimethylsiloxane and firming agent Mass ratio be 10:1.Described slurry is uniformly coated to silicon template surface, after Vacuum Degassing Process, uses and rotate painting Unnecessary slurry is removed by the mode covered, and forms one layer of thin polydimethylsiloxane liquid film.By whole template at 85 DEG C After environment solidifies 1 hour, PDMS membrane is peeled off from silicon template, makes side surface configuration height of projection Semiconductor composite thin film (thickness is 150um) for the micro-nano concaveconvex structure of 500nm.

2. the preparation of friction generator

Use the Copper Foil of thickness 100 μm as the second electrode lay 13.It is provided with wiener according to the first polymer material layer 12 The second electrode lay 13, towards the second electrode lay 13, is stacked on the first polymer material layer 12, obtains by the surface of concaveconvex structure Friction generator 9#.The edge of this friction generator seals with common adhesive plaster.

This friction generator is at I-V(current-voltage) measurement in show typical open circuit feature.Make under 1M Ω load (friction generator works for the bending of friction generator generating period and release, the open-circuit voltage of friction generator and work internal resistance Internal resistance can obtain by the way of triboelectricity resistance under duty by directly measuring) it is respectively 100V and 90M Ω.

Embodiment 10

1. the preparation of semiconductor composite

Use 1g sodium lauryl sulphate 50g Argent grain (average volume particle diameter 50 μm) is carried out surface process, obtain through Cross modifier surface modified metallic particles.By this through modifier surface modified metallic particles 30g, firming agent (DOW CORNING 184) join in 50g polydimethylsiloxane (DOW CORNING), obtain mixed slurry, wherein polydimethylsiloxane and firming agent Mass ratio be 10:1.Described slurry is uniformly coated to silicon template surface, after Vacuum Degassing Process, uses and rotate painting Unnecessary slurry is removed by the mode covered, and forms one layer of thin polydimethylsiloxane liquid film.By whole template at 85 DEG C After environment solidifies 1 hour, PDMS membrane is peeled off from silicon template, makes side surface configuration height of projection Semiconductor composite thin film (thickness is 150um) for the micro-nano concaveconvex structure of 500nm.

2. the preparation of friction generator

Use the Copper Foil of thickness 100 μm as the second electrode lay 13.It is provided with wiener according to the first polymer material layer 12 The second electrode lay 13, towards the second electrode lay 13, is stacked on the first polymer material layer 12, obtains by the surface of concaveconvex structure Friction generator 10#.The edge of this friction generator seals with common adhesive plaster.

This friction generator is at I-V(current-voltage) measurement in show typical open circuit feature.Make under 1M Ω load (friction generator works for the bending of friction generator generating period and release, the open-circuit voltage of friction generator and work internal resistance Internal resistance can obtain by the way of triboelectricity resistance under duty by directly measuring) it is respectively 75V and 35M Ω.

Embodiment 11

1. the preparation of semiconductor composite

Use 1g sodium lauryl sulphate 30g Argent grain (average volume particle diameter 50 μm) is carried out surface process, obtain through Cross modifier surface modified metallic particles.By this through modifier surface modified metallic particles 10g, firming agent (DOW CORNING 184) join in 90g polydimethylsiloxane (DOW CORNING), obtain mixed slurry, wherein polydimethylsiloxane and firming agent Mass ratio be 10:1.Described slurry is uniformly coated to silicon template surface, after Vacuum Degassing Process, uses and rotate painting Unnecessary slurry is removed by the mode covered, and forms one layer of thin polydimethylsiloxane liquid film.By whole template at 85 DEG C After environment solidifies 1 hour, PDMS membrane is peeled off from silicon template, makes side surface configuration height of projection Semiconductor composite thin film (thickness is 150um) for the micro-nano concaveconvex structure of 500nm.

2. the preparation of friction generator

Use the Copper Foil of thickness 100 μm as the second electrode lay 13.It is provided with wiener according to the first polymer material layer 12 The second electrode lay 13, towards the second electrode lay 13, is stacked on the first polymer material layer 12, obtains by the surface of concaveconvex structure Friction generator 11#.The edge of this friction generator seals with common adhesive plaster.

This friction generator is at I-V(current-voltage) measurement in show typical open circuit feature.Make under 1M Ω load (friction generator works for the bending of friction generator generating period and release, the open-circuit voltage of friction generator and work internal resistance Internal resistance can obtain by the way of triboelectricity resistance under duty by directly measuring) it is respectively 110V and 75M Ω.

Doped conducting metal granule in the polymer, can be effectively improved the electrical properties of polymer composites, permissible Effectively reduce the work internal resistance of friction generator.When metallic particles doping is gradually increased, owing to polymer composite material is quiet Electrical property is significantly affected, and the output performance of friction generator can present rapid decrease trend.Meanwhile, use modifying agent to gold The surface nature of metal particles is modified, and can be effectively improved metallic particles dispersion effect in the polymer, thus ensure poly- Compound composite material stable in properties, homogeneity.

The basic structure of the friction generator that Fig. 9, Figure 10, Figure 11, Figure 12 are used is identical with embodiment 1-11, a size of 3cm × 3cm, gross thickness is about 500 μm, and difference is polymer material layer.Fig. 9 is for using Cu doping 1wt% polymer (polydimethylsiloxane) semiconductor composite is the open-circuit voltage output valve of the friction generator of polymer material layer, Figure 10 The 1M Ω load voltage of the friction generator that 1wt% polymer semiconductor composite is polymer material layer for using Cu to adulterate Output valve.Figure 11 is the open circuit electricity of the friction generator of conventional polymeric materials layer (polydimethylsiloxane, undope metal) Pressure output valve.Figure 12 is the 1M Ω of the friction generator of conventional polymeric materials layer (polydimethylsiloxane, undope metal) Load voltage output valve.

Comparison diagram 9 and Figure 11, and Figure 10 and Figure 12 is it can be seen that the semiconductor composite layer of doping metals granule changes It is apt to the load capacity of friction generator.As can be seen here, the semiconductor composite layer of appropriate metallic particles of adulterating will effectively change The load capacity of kind friction generator, i.e. can improve the friction generator fan-out capability to low impedance circuit.

Claims

1. the friction generator applying semiconductor composite, it is characterised in that include the first electrode layer that stacking is arranged, First polymer material layer, and the second electrode lay, wherein the first polymer material layer material therefor is metal doped polymer Semiconductor composite.

Friction generator the most according to claim 1, it is characterised in that the first polymer material layer and the second electrode lay phase Micro-nano concaveconvex structure is set at least one face in two faces arranged, described first polymer material layer surface is arranged The micro-nano concaveconvex structure that micro-nano concaveconvex structure is height of projection 200nm-100 μm；Arrange on described the second electrode lay surface Micro-nano concaveconvex structure is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

Friction generator the most according to claim 1 and 2, it is characterised in that the first electrode layer material therefor is indium stannum oxygen Compound, Graphene, nano silver wire film, metal or alloy, wherein metal be Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, stannum, ferrum, Manganese, molybdenum, tungsten or vanadium；Alloy is aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, lead Alloy, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy；

The second electrode lay material therefor is metal or alloy, wherein metal can be Au Ag Pt Pd, aluminum, nickel, copper, titanium, chromium, Stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy can be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese conjunction Gold, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum Alloy.

Friction generator the most according to claim 1, it is characterised in that described friction generator farther includes second and gathers Laminate material layer, this second polymer material layer is arranged between the first polymer material layer and the second electrode lay.

Friction generator the most according to claim 4, it is characterised in that the first polymer material layer and the second polymeric material Micro-nano concaveconvex structure is set at least one face in two faces that the bed of material is oppositely arranged, described first polymer material layer and/ Or the second concavo-convex knot of the micro-nano that micro-nano concaveconvex structure is height of projection 200nm-100 μm arranged on polymer material layer surface Structure.

6. according to the friction generator described in claim 4 or 5, it is characterised in that material used by described second polymer material layer Material is the semiconductor composite of metal doped polymer.

7. according to the friction generator described in claim 4 or 5, it is characterised in that material used by described second polymer material layer Material is Kapton, aniline-formaldehyde resin thin film, polyformaldehyde thin film, ethyl cellulose film, polyamide film, melamine Amine formaldehyde thin film, Polyethylene Glycol succinate thin film, cellulose membrane, cellulose acetate film, 10PE27 Thin film, polydiallyl phthalate thin film, cellulose sponge thin film, renewable sponge thin film, elastic polyurethane body thin film, benzene Ethylene propylene copolymer thin film, styrene-butadiene-copolymer thin film, staple fibre thin film, polymethyl methacrylate film, Polyvinyl alcohol film, polyisobutylene thin film, pet film, polyvinyl butyral film, formaldehyde benzene Phenol condensation polymer thin film, neoprene thin film, butadiene-propylene copolymer thin film, natural rubber films, polyacrylonitrile thin film, propylene Any one in nitrile vinyl chloride copolymer thin film.

Friction generator the most according to claim 4, it is characterised in that described friction generator farther includes electricity between two parties Pole layer, described intervening electrode layer is arranged between the first polymer material layer and the second polymer material layer.

Friction generator the most according to claim 6, it is characterised in that described friction generator farther includes electricity between two parties Pole layer, described intervening electrode layer is arranged between the first polymer material layer and the second polymer material layer.

Friction generator the most according to claim 8 or claim 9, it is characterised in that described intervening electrode layer is metal, metal Oxide, alloy-layer, or patterned metal line-high polymer layer stack, wherein metal be Au Ag Pt Pd, aluminum, nickel, Copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, Manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy Or tantalum alloy, metal-oxide is indium tin oxide.

11. friction generator according to claim 8 or claim 9, it is characterised in that the first polymer material layer and intervening electrode On at least one face in two faces that layer is oppositely arranged, and/or the second polymer material layer and intervening electrode layer are oppositely arranged Two faces at least one face on micro-nano concaveconvex structure is set, described micro-nano concaveconvex structure is height of projection 200nm-100 μ The micro-nano concaveconvex structure of m.

12. friction generator according to claim 10, it is characterised in that the first polymer material layer and intervening electrode layer On at least one face in two faces being oppositely arranged, and/or the second polymer material layer and intervening electrode layer are oppositely arranged Arranging micro-nano concaveconvex structure at least one face in two faces, described micro-nano concaveconvex structure is height of projection 200nm-100 μm Micro-nano concaveconvex structure.

13. according to the friction generator described in claim 4,8 or 9, it is characterised in that the first electrode layer and the second electrode lay institute Indium tin oxide, Graphene, nano silver wire film, metal or alloy with material, wherein metal be Au Ag Pt Pd, aluminum, nickel, Copper, titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, Manganese alloy, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy Or tantalum alloy.

14. according to the friction generator described in claim 1,4,8 or 9, it is characterised in that in parts by weight, described quasiconductor Composite includes metallic particles 1-50 part, and polymeric base material 30-99 part.

15. friction generator according to claim 6, it is characterised in that in parts by weight, described semiconductor composite Including metallic particles 1-50 part, and polymeric base material 30-99 part.

16. friction generator according to claim 14, it is characterised in that in parts by weight, described semiconductors coupling material Material includes metallic particles 1-10 part, and polymeric base material 90-99 part.

17. friction generator according to claim 15, it is characterised in that in parts by weight, described semiconductors coupling material Material includes metallic particles 1-10 part, and polymeric base material 90-99 part.

18. friction generator according to claim 14, it is characterised in that described polymeric base material is poly dimethyl Siloxanes, Kynoar, polymethyl methacrylate or polrvinyl chloride.

19. according to the friction generator described in claim 15,16 or 17, it is characterised in that described polymeric base material is Polydimethylsiloxane, Kynoar, polymethyl methacrylate or polrvinyl chloride.

20. friction generator according to claim 14, it is characterised in that described metallic particles be silver, copper, gold, aluminum, At least one in tungsten, nickel, ferrum, its particle volume diameter is in 1-100 μm.

21. according to the friction generator described in claim 15,16,17 or 18, it is characterised in that described metallic particles be silver, At least one in copper, gold, aluminum, tungsten, nickel, ferrum, its particle volume diameter is in 1-100 μm.

22. friction generator according to claim 19, it is characterised in that described metallic particles be silver, copper, gold, aluminum, At least one in tungsten, nickel, ferrum, its particle volume diameter is in 1-100 μm.

23. according to the friction generator described in claim 20 or 22, it is characterised in that described metallic particles is through modifying agent The metallic particles of surface modification, metallic particles is 1-50:1 with the weight ratio of modifying agent.

24. friction generator according to claim 21, it is characterised in that described metallic particles is through Modifiers Surface Modified metallic particles, metallic particles is 1-50:1 with the weight ratio of modifying agent.

25. friction generator according to claim 23, it is characterised in that described metallic particles and the weight ratio of modifying agent For 1-30:1.

26. friction generator according to claim 24, it is characterised in that described metallic particles and the weight ratio of modifying agent For 1-30:1.

27. friction generator according to claim 23, it is characterised in that described modifying agent be polyvinylpyrrolidone, Cetyl trimethylammonium bromide, dioctadecyl dimethyl ammonium chloride, sodium laurate, enuatrol, sodium lauryl sulphate, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silane, gamma-chloropropylmethyldimethoxysilane, vinyl three second TMOS, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, β-(3,4 epoxide rings Hexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxysilane alkane, γ-mercaptopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-(3,2 glycidoxy) MTMS, gamma-mercaptopropyltriethoxysilane, γ-(ethylenediamine base) propyl trimethoxy silicane, γ-ammonia third Ethyl triethoxy silicane alkane, double-[3-(triethoxy) silicon propyl group tetrasulfide, diethylenetriamine base propyl trimethoxy silicane, γ-ethylenediamine ethyl triethoxy silicane alkane, Α-(ethylenediamine base) MTES, anilinomethyl triethoxysilane, benzene Amine MTMS, double (3-triethoxysilylpropyltetrasulfide) four nitric sulfids, Cyclohexyl Methyl Dimethoxysilane, Tetra-n-butyl titanate, tetraisopropoxy titanium, 2-ethyl-1-hexanol titanium, metatitanic acid four n-propyl, poly(tributoxy titanium), isopropyl two oil Acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isopropyl three oil Acid acyloxy titanate esters, isopropyl three (dodecyl benzenesulfonyl) titanate esters, three stearic acid isopropyl titanates, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters, tetra isopropyl two (dioctyl Phosphorous acid acyloxy) titanate esters, double (levulinic ketone group) (diisopropyl) titanate esters, double (levulinic ketone groups) (isobutoxy is different Propoxyl group) titanate esters, double (levulinic ketone group) (ethyoxyl isopropoxy) titanate esters, two (triethanolamine) metatitanic acid diisopropyl ester, 2,2 ', 2 " at least one in-nitrilo triethyl group titanate esters, double (ethyl acetoacetate) metatitanic acid diisobutyl ester.

28. according to the friction generator described in any one of claim 24-26, it is characterised in that described modifying agent is polyethylene Ketopyrrolidine, cetyl trimethylammonium bromide, dioctadecyl dimethyl ammonium chloride, sodium laurate, enuatrol, dodecyl Sodium sulfate, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silane, gamma-chloropropylmethyldimethoxysilane, ethylene Ethyl triethoxy silicane alkane, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, β-(3,4 Epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxysilane alkane, γ-mercapto propyl trimethoxy Silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-(3,2 epoxies third Epoxide) MTMS, gamma-mercaptopropyltriethoxysilane, γ-(ethylenediamine base) propyl trimethoxy silicane, γ- Aminopropyl triethoxysilane, double-[3-(triethoxy) silicon propyl group tetrasulfide, diethylenetriamine base propyl trimethoxy silicon Alkane, γ-ethylenediamine ethyl triethoxy silicane alkane, Α-(ethylenediamine base) MTES, anilinomethyl triethoxysilicane Alkane, anilinomethyl trimethoxy silane, double (3-triethoxysilylpropyltetrasulfide) four nitric sulfids, cyclohexyl methyl dimethoxy Silane, tetra-n-butyl titanate, tetraisopropoxy titanium, 2-ethyl-1-hexanol titanium, metatitanic acid four n-propyl, poly(tributoxy titanium), isopropyl Two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isopropyl Three oleic acid acyloxy titanate esters, isopropyl three (dodecyl benzenesulfonyl) titanate esters, three stearic acid isopropyl titanates, isopropyl Three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters, (two is pungent for tetra isopropyl two Base phosphorous acid acyloxy) titanate esters, double (levulinic ketone group) (diisopropyl) titanate esters, double (levulinic ketone group) (isobutoxy Isopropoxy) titanate esters, double (levulinic ketone group) (ethyoxyl isopropoxy) titanate esters, two (triethanolamine) metatitanic acid diisopropyl Ester, 2,2 ', 2 "-nitrilo triethyl group titanate esters, at least one in double (ethyl acetoacetate) metatitanic acid diisobutyl ester.

29. friction generator according to claim 27, it is characterised in that described modifying agent is sodium lauryl sulphate.

30. friction generator according to claim 28, it is characterised in that described modifying agent is sodium lauryl sulphate.

31. 1 kinds of friction generator, it is characterised in that include the first electrode layer that stacking is arranged, the first polymer material layer, occupy Between thin layer, the second polymer material layer and the second electrode lay, wherein, in the first polymer material layer and between two parties thin layer extremely Few one layer, and/or the second polymer material layer and between two parties at least one of which material therefor in thin layer be metal doped polymer Semiconductor composite.

32. friction generator according to claim 31, it is characterised in that in parts by weight, described semiconductors coupling material Material includes metallic particles 1-50 part, and polymeric base material 30-99 part.

33. friction generator according to claim 32, it is characterised in that in parts by weight, described semiconductors coupling material Material includes metallic particles 1-10 part, and polymeric base material 90-99 part.

34. according to the friction generator described in claim 32 or 33, it is characterised in that described polymeric base material is poly-two Methylsiloxane, Kynoar, polymethyl methacrylate or polrvinyl chloride.

35. according to the friction generator described in claim 32 or 33, it is characterised in that described metallic particles be silver, copper, gold, At least one in aluminum, tungsten, nickel, ferrum, its particle volume diameter is in 1-100 μm.

36. friction generator according to claim 35, it is characterised in that described metallic particles is through Modifiers Surface Modified metallic particles, metallic particles is 1-50:1 with the weight ratio of modifying agent.

37. friction generator according to claim 36, it is characterised in that described metallic particles and the weight ratio of modifying agent For 1-30:1.

38. according to the friction generator described in claim 36 or 37, it is characterised in that described modifying agent is polyvinylpyrrolidine Ketone, cetyl trimethylammonium bromide, dioctadecyl dimethyl ammonium chloride, sodium laurate, enuatrol, lauryl sulphate acid Sodium, γ-chloropropyl trichloro-silane, γ-r-chloropropyl trimethoxyl silane, gamma-chloropropylmethyldimethoxysilane, vinyl three Ethoxysilane, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, β-(3,4 epoxies Cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxysilane alkane, γ-mercapto propyl trimethoxy silicon Alkane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-(3,2 epoxy the third oxygen Base) MTMS, gamma-mercaptopropyltriethoxysilane, γ-(ethylenediamine base) propyl trimethoxy silicane, γ-ammonia Propyl-triethoxysilicane, double-[3-(triethoxy) silicon propyl group tetrasulfide, diethylenetriamine base propyl trimethoxy silicane, γ-ethylenediamine ethyl triethoxy silicane alkane, Α-(ethylenediamine base) MTES, anilinomethyl triethoxysilane, benzene Amine MTMS, double (3-triethoxysilylpropyltetrasulfide) four nitric sulfids, Cyclohexyl Methyl Dimethoxysilane, Tetra-n-butyl titanate, tetraisopropoxy titanium, 2-ethyl-1-hexanol titanium, metatitanic acid four n-propyl, poly(tributoxy titanium), isopropyl two oil Acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isopropyl three oil Acid acyloxy titanate esters, isopropyl three (dodecyl benzenesulfonyl) titanate esters, three stearic acid isopropyl titanates, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters, tetra isopropyl two (dioctyl Phosphorous acid acyloxy) titanate esters, double (levulinic ketone group) (diisopropyl) titanate esters, double (levulinic ketone groups) (isobutoxy is different Propoxyl group) titanate esters, double (levulinic ketone group) (ethyoxyl isopropoxy) titanate esters, two (triethanolamine) metatitanic acid diisopropyl ester, 2,2 ', 2 " at least one in-nitrilo triethyl group titanate esters, double (ethyl acetoacetate) metatitanic acid diisobutyl ester.

39. according to the friction generator described in claim 38, it is characterised in that described modifying agent is sodium lauryl sulphate.

40. friction generator according to claim 31, it is characterised in that the first polymer material layer and between two parties thin layer Micro-nano concaveconvex structure is set at least one face in two faces being oppositely arranged, and/or the second polymer material layer and between two parties On at least one face in two faces that thin layer is oppositely arranged, micro-nano concaveconvex structure is set；

Arrange on described first polymer material layer, and/or thin layer between two parties, and/or the second polymer material layer surface is micro- Concaveconvex structure of receiving is the micro-nano concaveconvex structure of height of projection 200nm-100 μm.

41. friction generator according to claim 31, it is characterised in that material used by the first electrode layer and the second electrode lay Material is indium tin oxide, Graphene, nano silver wire film, metal or alloy, wherein metal be Au Ag Pt Pd, aluminum, nickel, copper, Titanium, chromium, stannum, ferrum, manganese, molybdenum, tungsten or vanadium；Alloy is aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese conjunction Gold, nickel alloy, metal, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum Alloy.

42. friction generator according to claim 31, it is characterised in that when the first polymer material layer or the thinnest Film layer, or when the second polymer material layer does not uses semiconductor composite, its material therefor is selected from Kapton, aniline Formaldehyde resin thin film, polyformaldehyde thin film, ethyl cellulose film, polyamide film, melamino-formaldehyde thin film, Polyethylene Glycol fourth Diacid ester film, cellulose membrane, cellulose acetate film, 10PE27 thin film, poly-diallyl phthalate Propyl ester thin film, cellulose sponge thin film, renewable sponge thin film, elastic polyurethane body thin film, styrene-acrylonitrile copolymer copolymer film, benzene Ethylene butadiene copolymers thin film, staple fibre thin film, polymethyl methacrylate film, polyvinyl alcohol film, polyisobutylene Thin film, pet film, polyvinyl butyral film, formaldehyde-phenol condensation polymer thin film, neoprene In thin film, butadiene-propylene copolymer thin film, natural rubber films, polyacrylonitrile thin film, acrylonitrile vinyl chloride copolymer thin film Any one.