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Número de publicaciónCN104426416 A
Tipo de publicaciónSolicitud
Número de solicitudCN 201310389137
Fecha de publicación18 Mar 2015
Fecha de presentación30 Ago 2013
Fecha de prioridad30 Ago 2013
También publicado comoCN104426416B
Número de publicación201310389137.6, CN 104426416 A, CN 104426416A, CN 201310389137, CN-A-104426416, CN104426416 A, CN104426416A, CN201310389137, CN201310389137.6
Inventores殷亮, 李洁, 王竹, 赵豪
Solicitante纳米新能源(唐山)有限责任公司
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Friction power generator employing semiconductor composite material
CN 104426416 A
Resumen
The invention provides a friction power generator employing a semiconductor composite material. The friction power generator comprises a first electrode layer, a first polymer material layer and a second electrode layer, which are laminated, wherein a material for the first polymer material layer is a metal-doped polymer semiconductor composite material. According to the friction power generator, an insulating polymer is doped with metal particles, so that the resistivity of the polymer is reduced, and the volume resistivity of the polymer is at a level between the volume resistivity of metal and the volume resistivity of an insulating material. According to the friction power generator, the working internal resistance of the power generator can be effectively reduced, and the load capacity of the friction power generator can be improved within a certain range.
Reclamaciones(31)  traducido del chino
1. 一种应用半导体复合材料的摩擦发电机,其特征在于,包括层叠设置的第一电极层, 第一聚合物材料层,和第二电极层,其中第一聚合物材料层所用材料是金属掺杂聚合物的半导体复合材料。 A semiconductor composite friction application generator, characterized in that the laminate comprises a first electrode layer disposed, a first layer of polymeric material, and a second electrode layer, wherein the first layer of polymeric material is a metal material used doped semiconductor composite polymer.
2. 根据权利要求1所述的摩擦发电机,其特征在于,第一聚合物材料层和第二电极层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述第一聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100iim的微纳凹凸结构;所述第二电极层表面上设置的微纳凹凸结构为凸起高度200nm-100iim的微纳凹凸结构。 Friction generator according to claim 1, characterized in that the two faces of the first polymeric material layer and a second electrode layer disposed opposite at least one surface relief micro-nano structure disposed, the first Micronanoelectronic convex structure layer of polymeric material disposed on the surface of a convex micro-nano convex structure height of 200nm-100iim; Micronanoelectronic uneven structure of the second electrode layer disposed on the surface of the bump height 200nm-100iim Micronanoelectronic irregularities structure.
3. 根据权利要求1或2所述的摩擦发电机,其特征在于,第一电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、 猛、钥、鹤或钥;;合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金; 第二电极层所用材料是金属或合金,其中金属可以是金、银、钼、钯、铝、镍、铜、钛、铬、 锡、铁、猛、钥、鹤或钥;;合金可以是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 3. The friction generator 1 or claim 2, wherein, characterized in that the material for the first electrode layer is indium tin oxide, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, fierce, key, key ;; crane or alloy is wrong alloys, titanium alloys, magnesium alloys, beryllium alloys, copper, zinc alloy, alloy fierce, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys; a second electrode layer material is a metal or alloy, wherein the metal may be gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, fierce, key, key ;; crane or alloys may be wrong alloys, titanium, magnesium alloys, beryllium alloys, copper, zinc alloy, Meng alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.
4. 根据权利要求1所述的摩擦发电机,其特征在于,所述摩擦发电机进一步包括第二聚合物材料层,该第二聚合物材料层设置在第一聚合物材料层和第二电极层之间。 Friction generator according to claim 1, characterized in that said friction generator further comprises a second layer of polymeric material, the second layer of polymeric material disposed on the first electrode layer and the second polymeric material between the layers.
5. 根据权利要求4所述的摩擦发电机,其特征在于,第一聚合物材料层和第二聚合物材料层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述第一聚合物材料层和/或第二聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100 ii m的微纳凹凸结构。 Friction generator according to claim 4, characterized in that the two faces of the first polymeric material layer and the second layer of polymeric material disposed opposite at least one surface relief micro-nano structure disposed, the Micronanoelectronic uneven structure provided on material layer and / or the second surface of the first layer of polymeric material polymer bump height 200nm-100 ii m of micro-nano convex structure.
6. 根据权利要求4或5所述的摩擦发电机,其特征在于,所述第二聚合物材料层所用材料是金属掺杂聚合物的半导体复合材料。 Friction generator according to claim 4 or 5, characterized in that said second layer of polymeric material used for the polymer material is a metal-doped semiconductor composite.
7. 根据权利要求4或5所述的摩擦发电机,其特征在于,所述第二聚合物材料层所用材料是聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、 聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 According to 4 or 5, wherein the friction generator as claimed in claim wherein said second layer of polymeric material material used is a polyimide film, an aniline-formaldehyde resin film, a polyoxymethylene film, ethylcellulose film , a polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, cellulose film, cellulose acetate film, polyethylene adipate film, polyethylene film diallyl phthalate cellulose sponge film, regenerated sponge film, a polyurethane elastomer film, styrene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, a polyvinyl alcohol film, polyisobutylene film, polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film, a natural rubber film, polyacrylonitrile film, propylene nitrile chloride copolymer film of any one.
8. 根据权利要求4-7任一项所述的摩擦发电机,其特征在于,所述摩擦发电机进一步包括居间电极层,所述居间电极层设置在第一聚合物材料层和第二聚合物材料层之间。 According to claim any one of claims 4-7 frictional generator, wherein said generator further comprises a friction intervening electrode layers, said intervening layer is disposed on the first electrode layer and the second polymeric material polymerization between the material layers.
9. 根据权利要求8所述的摩擦发电机,其特征在于,所述居间电极层为金属、金属氧化物、合金层,或图形化金属线-高分子聚合物层叠体,其中金属是金、银、钼、钯、铝、镍、铜、 钛、铬、锡、铁、猛、钥、鹤或钥;;合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金,金属氧化物为铟锡氧化物。 Friction generator according to claim 8, characterized in that the intermediate electrode layer is a metal, a metal oxide, an alloy layer, or a patterned metal wire - polymer stacked body, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, fierce, key, key ;; crane or alloy is wrong alloys, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, Meng alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloy, a metal oxide is indium tin oxide.
10. 根据权利要求8或9所述的摩擦发电机,其特征在于,第一聚合物材料层和居间电极层相对设置的两个面中的至少一个面上,和/或第二聚合物材料层和居间电极层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述微纳凹凸结构为凸起高度200nm-100iim的微纳凹凸结构。 According to claim 8 or 9, wherein the friction generator, characterized in that the at least one surface of two surfaces and an intervening layer of a first polymeric material layer opposite electrode disposed in, and / or the second polymeric material Two surface layers and intervening electrode layer disposed opposite at least one surface uneven structure set up micro-nano, micro and nano convex structure of the convex micro-nano convex structure height of 200nm-100iim.
11. 根据权利要求4-10任一项所述的摩擦发电机,其特征在于,第一电极层和第二电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、 铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或1凡;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 According to one of claims 4-10 generator according to any friction, characterized in that the first electrode layer and the second electrode layer is indium tin oxide material, graphene, silver nanowire film, a metal or alloy wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or 1 Fan; alloys are aluminum, titanium, magnesium alloys, beryllium alloys, copper alloy, zinc alloy, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.
12. 根据权利要求1-11任一项所述的摩擦发电机,其特征在于,以重量份计,所述半导体复合材料包括金属颗粒1-50份,和聚合物基底材料30-99份。 According to one of claims 1-11 generator according to any friction, characterized in that, in parts by weight, the semiconductor composite metal particles comprising 1 to 50 parts, and 30-99 parts of polymer base material.
13. 根据权利要求12所述的摩擦发电机,其特征在于,以重量份计,所述半导体复合材料包括金属颗粒1-10份,和聚合物基底材料90-99份。 Friction generator according to claim 12, characterized in that, in parts by weight, the semiconductor composite metal particles comprising 1-10 parts, and 90-99 parts of polymer base material.
14. 根据权利要求12或13所述的摩擦发电机,其特征在于,所述聚合物基底材料是聚二甲基硅氧烷、聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯。 Friction power generator according to claim 12 or 13, characterized in that the polymer base material is a polydimethylsiloxane, polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride.
15. 根据权利要求12-14任一项所述的摩擦发电机,其特征在于,所述金属颗粒是银、 铜、金、铝、钨、镍、铁中的至少一种,其体积粒径在1-100 U m。 15. According to claims 12-14 wherein the generator according to any friction, characterized in that the metal particles are silver, at least one of copper, gold, aluminum, tungsten, nickel, iron, and its volume particle size In 1-100 U m.
16. 根据权利要求15所述的摩擦发电机,其特征在于,所述金属颗粒是经过改性剂表面改性的金属颗粒,金属颗粒与改性剂的重量比为1-50 :1。 Friction generator according to claim 15, characterized in that, after the metal particles are metal particles by weight of the surface-modified modifier, metallic particles with a modifier ratio 1-50: 1.
17. 根据权利要求16所述的摩擦发电机,其特征在于,所述金属颗粒与改性剂的重量比为1-30 :1。 Friction generator according to claim 16, characterized in that the weight of the metal particles and the ratio of modifier 1 to 30: 1.
18. 根据权利要求16或17所述的摩擦发电机,其特征在于,所述改性剂是聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵、月桂酸钠、油酸钠、十二烷基硫酸纳、Y _氣丙基二氣娃烧、Y _氣丙基二甲氧基娃烧、Y _氣丙基甲基-甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二甲氧基娃烧、(甲基丙稀醜氧基)丙基二甲氧基娃烧、¢- (3,4 环氧环己基)乙基三甲氧基硅烷、缩水甘油醚基丙基三甲氧基硅烷、巯丙基三甲氧基娃烧、(氣乙基氣丙基二甲氧基娃烧、脈基丙基二乙氧基娃烧、Y - (3, 2 环氧丙氧基)甲基三甲氧基硅烷、Y-巯丙基三乙氧基硅烷、Y-(乙二胺基)丙基三甲氧基娃烧、氛丙基二乙氧基娃烧、双-[3_ (二乙氧基)娃丙基四硫化物、二乙稀二胺基丙基二甲氧基娃烧、乙二胺基二乙氧基娃烧、A-(乙二胺基)甲基二乙氧基娃烧、苯胺甲基二乙氧基硅烷、苯胺甲基三甲氧基硅烷、双(3-三乙氧基甲硅烷基丙基)四硫化碳、环己基甲基二甲氧基硅烷、钛酸四正丁酯、四异丙氧基钛、2-乙基-1-己醇钛、钛酸四正丙酯、聚钛酸丁酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯、三硬脂酸钛酸异丙酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛基焦磷酸酰氧基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、双(乙酰丙酮基)(二异丙基)钛酸酯、双(乙酰丙酮基) (异丁氧基异丙氧基)钛酸酯、双(乙酰丙酮基)(乙氧基异丙氧基)钛酸酯、二(三乙醇胺)钛酸二异丙酯、2, 2',2"-氮基三乙基钛酸酯、双(乙酰乙酸乙酯)钛酸二异丁酯中的至少一种。 According to claim 16 or 17, wherein the friction generator, wherein said modifier is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, dioctadecyl dimethyl dichloride ammonium, sodium laurate, sodium oleate, sodium lauryl sulfate, Y _ two gas baby burn gas-propyl, Y _ gas propyldimethoxysilane baby burn, Y _ gas-propyl-methyl - methoxy baby burn, ethylene group diethoxy baby burn baby burn dimethoxy ethylene (meth acrylic ugly) propyl dimethoxy baby burn, ¢ - (3,4 epoxy ring hexyl) ethyl trimethoxysilane, glycidyl propyl trimethoxysilane, mercaptopropyl trimethoxysilane baby burn, (gas ethyl gas propyldimethoxysilane baby burn, pulse propyl diethoxy group baby burn, Y - (3, 2 epoxypropoxy) methyl trimethoxysilane, Y- mercapto propyl triethoxy silane, Y- (ethylenediamine-yl) propyl trimethoxy baby burn, propyl diethoxy baby burn atmosphere, bis - [3_ (diethoxy) propyl tetrasulfide baby, two ethylene diamino propyldimethoxysilane baby burn, ethylenediamino diethoxy baby burn, A- (ethylene diamine-yl) methyl diethoxy baby burn, aniline methyldiethoxysilane, aniline methyl trimethoxysilane, bis (3-triethoxysilyl propyl ) tetrasulfide carbon, cyclohexyl methyl dimethoxy silane, tetra-n-butyl titanate, titanium tetraisopropoxide, titanium 2-ethyl-1-hexanol, tetra-n-propyl titanate, poly butyl, isopropyl dioleate acyloxy (acyloxy dioctyl phosphate) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tri oleic acyloxy titanate, isopropyl tri (dodecylbenzene sulfonyl) titanate, isopropyl titanate tristearate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, bis (dioctyl pyrophosphate acyloxy) ethylene titanate, tetraisopropyl-bis (acyloxy octyl phosphate) titanate, bis (acetylacetonate) (diisopropyl) titanate ester, bis (acetylacetonato) (isobutoxy isopropoxy) titanate, bis (acetylacetonato) (ethoxy isopropoxy) titanate, bis (triethanolamine) titanate, di-iso- propyl, 2, 2 ', 2 "- nitrilotriacetic ethyl titanate, bis (ethylacetoacetate) at least one of diisobutyl titanate.
19. 根据权利要求18所述的摩擦发电机,其特征在于,所述改性剂是十二烷基硫酸钠。 Friction generator according to claim 18, characterized in that said modifier is sodium lauryl sulfate.
20. -种摩擦发电机,其特征在于,包括层叠设置的第一电极层,第一聚合物材料层,居间薄膜层,第二聚合物材料层和第二电极层,其中,第一聚合物材料层和居间薄膜层中的至少一层,和/或第二聚合物材料层和居间薄膜层中的至少一层所用材料是金属掺杂聚合物的半导体复合材料。 20. - species friction generator, characterized in that the laminate comprises a first electrode layer disposed, a first layer of polymeric material, intermediate film layer, a second layer of polymeric material and a second electrode layer, wherein the first polymer material layer and the intervening film layers at least one layer, and / or the second layer of polymeric material and intervening film layers at least one layer of semiconductor material used is metal-doped polymer composites.
21. 根据权利要求20所述的摩擦发电机,其特征在于,以重量份计,所述半导体复合材料包括金属颗粒1-50份,和聚合物基底材料30-99份。 21. A friction generator according to claim 20, characterized in that, in parts by weight, the semiconductor composite metal particles comprising 1 to 50 parts, and 30-99 parts of polymer base material.
22. 根据权利要求21所述的摩擦发电机,其特征在于,以重量份计,所述半导体复合材料包括金属颗粒1-10份,和聚合物基底材料90-99份。 22. A friction generator according to claim 21, wherein, in parts by weight, the semiconductor composite metal particles comprising 1-10 parts, and 90-99 parts of polymer base material.
23. 根据权利要求21或22所述的摩擦发电机,其特征在于,所述聚合物基底材料是聚二甲基硅氧烷、聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯。 23. A according to claim 21 or 22 wherein the friction generator, wherein said polymer base material is a polydimethylsiloxane, polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride.
24. 根据权利要求21-23任一项所述的摩擦发电机,其特征在于,所述金属颗粒是银、 铜、金、铝、钨、镍、铁中的至少一种,其体积粒径在1-100 U m。 24. The claims 21-23 wherein the generator according to any friction, characterized in that the metal particles are silver, at least one of copper, gold, aluminum, tungsten, nickel, iron, and its volume particle size In 1-100 U m.
25. 根据权利要求24所述的摩擦发电机,其特征在于,所述金属颗粒是经过改性剂表面改性的金属颗粒,金属颗粒与改性剂的重量比为1-50 :1。 25. A friction generator according to claim 24, characterized in that, after the metal particles are metal particles by weight of the surface-modified modifier, metallic particles with a modifier ratio 1-50: 1.
26. 根据权利要求25所述的摩擦发电机,其特征在于,所述金属颗粒与改性剂的重量比为1-30 :1。 26. A friction generator according to claim 25, characterized in that the weight of the metal particles and the ratio of modifier 1 to 30: 1.
27. 根据权利要求25或26所述的摩擦发电机,其特征在于,所述改性剂是聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵、月桂酸钠、油酸钠、十二烷基硫酸纳、Y _氣丙基二氣娃烧、Y _氣丙基二甲氧基娃烧、Y _氣丙基甲基-甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二甲氧基娃烧、(甲基丙稀醜氧基)丙基二甲氧基娃烧、¢- (3,4 环氧环己基)乙基三甲氧基硅烷、缩水甘油醚基丙基三甲氧基硅烷、巯丙基三甲氧基娃烧、(氣乙基氣丙基二甲氧基娃烧、脈基丙基二乙氧基娃烧、Y - (3, 2 环氧丙氧基)甲基三甲氧基硅烷、Y-巯丙基三乙氧基硅烷、Y-(乙二胺基)丙基三甲氧基娃烧、Y _氛丙基二乙氧基娃烧、双-[3_ (二乙氧基)娃丙基四硫化物、二乙稀二胺基丙基二甲氧基娃烧、乙二胺基二乙氧基娃烧、A-(乙二胺基)甲基二乙氧基娃烧、苯胺甲基二乙氧基硅烷、苯胺甲基三甲氧基硅烷、双(3-三乙氧基甲硅烷基丙基)四硫化碳、环己基甲基二甲氧基硅烷、钛酸四正丁酯、四异丙氧基钛、2-乙基-1-己醇钛、钛酸四正丙酯、聚钛酸丁酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯、三硬脂酸钛酸异丙酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛基焦磷酸酰氧基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、双(乙酰丙酮基)(二异丙基)钛酸酯、双(乙酰丙酮基) (异丁氧基异丙氧基)钛酸酯、双(乙酰丙酮基)(乙氧基异丙氧基)钛酸酯、二(三乙醇胺)钛酸二异丙酯、2, 2',2"-氮基三乙基钛酸酯、双(乙酰乙酸乙酯)钛酸二异丁酯中的至少一种。 27. The 25 or 26, wherein the friction generator of claim wherein said modifier is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, distearyl dimethyl dichloride ammonium, sodium laurate, sodium oleate, sodium lauryl sulfate, Y _ two gas baby burn gas-propyl, Y _ gas propyldimethoxysilane baby burn, Y _ gas-propyl-methyl - methoxy baby burn, ethylene group diethoxy baby burn baby burn dimethoxy ethylene (meth acrylic ugly) propyl dimethoxy baby burn, ¢ - (3,4 epoxy ring hexyl) ethyl trimethoxysilane, glycidyl propyl trimethoxysilane, mercaptopropyl trimethoxysilane baby burn, (gas ethyl gas propyldimethoxysilane baby burn, pulse propyl diethoxy group baby burn, Y - (3, 2 epoxypropoxy) methyl trimethoxysilane, Y- mercapto propyl triethoxy silane, Y- (ethylenediamine-yl) propyl trimethoxy baby burn, Y _ diethoxy propyl baby burn atmosphere, bis - [3_ (diethoxy) propyl tetrasulfide baby, two ethylene diamino propyldimethoxysilane baby burn, ethylenediamine diacetate oxy baby burn, A- (ethylene diamine-yl) methyl diethoxy baby burn, aniline methyldiethoxysilane, aniline methyl trimethoxysilane, bis (3-triethoxysilyl group propyl) tetrasulfide carbon, cyclohexyl methyl dimethoxy silane, tetra-n-butyl titanate, titanium tetraisopropoxide, titanium 2-ethyl-1-hexanol, tetra-n-propyl, poly tetrabutyl titanate, isopropyl dioleate acyloxy (acyloxy dioctyl phosphate) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tri oleate acyloxy titanate, isopropyl tri (dodecylbenzene sulfonyl) titanate, isopropyl titanate tristearate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate ester, bis (dioctyl pyrophosphate acyloxy) ethylene titanate, tetraisopropyl-bis (acyloxy octyl phosphate) titanate, bis (acetylacetonate) (diisopropyl) titanate, bis (acetylacetonato) (isobutoxy isopropoxy) titanate, bis (acetylacetonato) (ethoxy isopropoxy) titanate, bis (triethanolamine) titanate diisopropyl, 2, 2 ', 2 "- nitrilotriacetic ethyl titanate, at least one bis (ethylacetoacetate) diisobutyl titanate in.
28. 根据权利要求27所述的摩擦发电机,其特征在于,所述改性剂是十二烷基硫酸钠。 28. A friction generator according to claim 27, characterized in that said modifier is sodium lauryl sulfate.
29. 根据权利要求20-28任一项所述的摩擦发电机,其特征在于,第一聚合物材料层和居间薄膜层相对设置的两个面中的至少一个面上设置微纳凹凸结构,和/或第二聚合物材料层和居间薄膜层相对设置的两个面中的至少一个面上设置微纳凹凸结构; 所述第一聚合物材料层,和/或居间薄膜层,和/或第二聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100iim的微纳凹凸结构。 29. The claims 20-28 wherein the generator according to any friction, characterized in that the two faces of the first material layer and the intervening polymeric film layer opposite the surface provided with at least one micro-nano concavo-convex structure, and at least one surface of two surfaces / or the second layer of polymeric material and intervening film layers of oppositely disposed concave-convex structure set up micro-nano; the first layer of polymeric material, and / or intervening film layer, and / or Micronanoelectronic uneven structure provided on the second layer of polymeric material surface is raised height 200nm-100iim of micro-nano convex structure.
30. 根据权利要求20-29任一项所述的摩擦发电机,其特征在于,第一电极层和第二电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、 铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或|凡;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 30. The claims 20-29 wherein the generator according to any friction, characterized in that the first electrode layer and the second electrode layer is indium tin oxide material, graphene, silver nanowire film, a metal or alloy wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or | Fan; alloys are aluminum, titanium, magnesium alloys, beryllium alloys, copper alloy, zinc alloy, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.
31.根据权利要求20-30任一项所述的摩擦发电机,其特征在于,当第一聚合物材料层,或居间薄膜层,或第二聚合物材料层不采用半导体复合材料时,其所用材料选自聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 31. According to one of the friction generator any one of claims 20-30, wherein, when the first layer of polymeric material, or intermediate film layer, or second layer of polymeric material is not used semiconductor composite material As used material is selected from polyimide film, aniline-formaldehyde resin film, a polyoxymethylene film, ethylcellulose film, a polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, a cellulose film, a cellulose acetate acetate film, polyethylene adipate film, polyethylene film diallyl phthalate, cellulose sponges, films, sponges reproducing film, a polyurethane elastomer film, styrene-propylene copolymer film, styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, a polyvinyl alcohol film, polyisobutylene film, polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films , neoprene film, a propylene-butadiene copolymer film, natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride copolymer film of any one.
Descripción  traducido del chino
应用半导体复合材料的摩擦发电机 Application of semiconductor composite friction generator

技术领域 TECHNICAL FIELD

[0001] 本发明涉及摩擦发电领域,尤其是涉及一种应用金属掺杂聚合物半导体复合材料的摩擦发电机。 [0001] The present invention relates to the field of power generation of friction, particularly to an application of the metal-doped polymer semiconductor composites friction generator.

背景技术 Background technique

[0002] 目前,能源问题是影响人类进步和可持续发展的重大课题之一。 [0002] Currently, the energy issue is one of the major issues affecting human progress and sustainable development. 各种围绕新能源开发、可重复利用再生能源的研究正在世界各地如火如荼地进行着。 All kinds around the new energy development, reusable study is the use of renewable energy around the world in full swing.

[0003] 采用摩擦技术构建的能量收集和转换装置,在自供电纳米系统中起关键作用。 [0003] The friction technology to build energy collection and conversion means, from the self-powered nanosystems a key role in. 并且,由于其具备环保、成本低、自驱动等特性,受到了广泛关注。 And, because of its with environmental protection, low cost, self-propelled and other characteristics, has been widespread concern. 随着王中林教授研究组研发的压电摩擦发电机实现机械能转换为电能以来,以压电和摩擦电为基础的不同结构和材料的摩擦发电机相继问世。 As Professor Wang Zhonglin research group developed a piezoelectric generator friction achieve mechanical energy is converted to electrical energy since, piezoelectric and triboelectric based structure and materials of different friction generator after another. 目前,摩擦发电机已能够驱动小型液晶显示屏、低功率发光二极管以及微型电子器件和模块等,但是发电机的输出性能仍然是制约其发展和应用的关键因素。 Currently, the friction generators have been able to drive a small liquid crystal display, low-power light emitting diodes and micro-electronic components and modules, but the output performance of the generator is still the key factor restricting its development and application.

发明内容 SUMMARY OF THE INVENTION

[0004] 本发明所要解决的技术问题是:克服现有摩擦发电机输出性能的缺陷,提供了一种金属掺杂聚合物半导体复合材料的摩擦发电机,可以明显提高摩擦发电机的负载能力。 [0004] The technical problem to be solved by the present invention are: to overcome the existing friction generator output performance deficiencies, there is provided a metal-doped polymer semiconductor composites friction generator, can significantly improve the load capacity of the friction generator.

[0005] 将导电金属颗粒添加到绝缘聚合物中,能够降低聚合物的电阻率,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平,从而得到金属掺杂聚合物的半导体复合材料。 [0005] The conductive metal particles are added to the insulating polymer, the resistivity of the polymer can be reduced, so that the volume resistivity and the volume resistivity between metal levels between the volume resistivity of the insulating material, thereby obtaining the metal-doped polymerization semiconductor composite material. 金属掺杂聚合物半导体复合材料既具备了金属颗粒的功能特性如导电性, 也具有聚合物材料优良的机械性能和可加工性。 Metal-doped polymer semiconductor composites only has the features of the metal particles, such as conductivity, also has a polymer material excellent mechanical properties and processability. 在摩擦发电机中使用半导体复合物材料可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 Using a semiconductor composite material in the generator can effectively reduce the friction resistance generator work, within a certain range can increase the friction of the generator load capacity.

[0006] 然而,金属颗粒与聚合物之间性质的差异,使两者的兼容性较差,从而容易引起金属颗粒的团聚,影响半导体复合材料的性能。 [0006] However, the nature of the difference between the metal particles and the polymer, so that the two of compatibility is poor, which tends to cause agglomeration of the metal particles, affect the performance of the semiconductor composites. 因此,需要对金属颗粒进行表面改性,使其能够稳定的分散在聚合物基质中。 Therefore, the metal particles to surface modification, it can be stably dispersed in the polymer matrix.

[0007] 为了解决上述技术问题,本发明提供的第一技术方案,一种应用半导体复合材料的摩擦发电机,包括层叠设置的第一电极层,第一聚合物材料层,和第二电极层,其中第一聚合物材料层所用材料是金属掺杂聚合物的半导体复合材料。 [0007] In order to solve the above problems, a first aspect of the present invention provides a semiconductor composite friction application generator comprises a first electrode layer disposed stacked, a first layer of polymeric material, and a second electrode layer wherein the first layer of polymeric material used for the polymer material is a metal-doped semiconductor composite.

[0008] 前述的摩擦发电机,第一聚合物材料层和第二电极层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述第一聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构;所述第二电极层表面上设置的微纳凹凸结构为凸起高度200nm-100ym的微纳凹凸结构。 [0008] The foregoing friction generators, the two faces of the first polymeric material layer and the second electrode layer is oppositely disposed at least one surface of the micro-nano convex structure disposed, is provided on the surface of a first polymer material layer Micronanoelectronic convex structure is raised micro-nano convex structure height of 200nm-100μm; Micronanoelectronic uneven structure provided on the second electrode layer surface bump height 200nm-100ym of micro-nano convex structure.

[0009] 前述的摩擦发电机,第一电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金; [0009] The foregoing friction generator, a first electrode layer is indium tin oxide material, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloys are aluminum, titanium, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy , secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys;

[0010] 第二电极层所用材料是金属或合金,其中金属可以是金、银、钼、钯、铝、镍、铜、钛、 铬、锡、铁、猛、钥、鹤或钥;;合金可以是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0010] The second electrode layer material is a metal or alloy, wherein the metal may be gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, fierce, keyhole, crane or alloy key ;; It may be wrong alloys, titanium, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.

[0011] 前述的摩擦发电机,所述摩擦发电机进一步包括第二聚合物材料层,该第二聚合物材料层设置在第一聚合物材料层和第二电极层之间。 [0011] The foregoing friction generator, said generator further comprising a second friction layer of polymeric material, the second layer of polymeric material is disposed between the first polymeric material layer and the second electrode layer.

[0012] 前述的摩擦发电机,第一聚合物材料层和第二聚合物材料层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述第一聚合物材料层和/或第二聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构。 [0012] The foregoing friction generator, both surfaces of the first layer of polymeric material and second polymeric material layer disposed opposite the at least one surface of the micro-nano concavo-convex structure disposed, said first layer of polymeric material and / Micronanoelectronic uneven structure or set on a second layer of polymeric material surface projection height of 200nm-100μm bump micro and nano structures.

[0013] 前述的摩擦发电机,所述第二聚合物材料层所用材料是金属掺杂聚合物的半导体复合材料。 [0013] The foregoing friction generator, said second layer of polymeric material used for the polymer material is a metal-doped semiconductor composite.

[0014] 前述的摩擦发电机,所述第二聚合物材料层所用材料是聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、 聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、 丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 [0014] The foregoing friction generator, said second layer of polymeric material material used is a polyimide film, an aniline-formaldehyde resin film, a polyoxymethylene film, ethyl cellulose film, a polyamide film, a melamine-formaldehyde film, poly glycol succinate film, cellulose film, cellulose acetate film, polyethylene adipate film, polyethylene film diallyl phthalate, cellulose sponges, films, sponges reproducing film, polyurethane elastomeric film, styrene-propylene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, a polyvinyl alcohol film, polyisobutylene films, polyethylene terephthalate ester film, polyvinyl butyral films, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film, a natural rubber film, polyacrylonitrile film, acrylonitrile-vinyl chloride copolymer film of any one species.

[0015] 前述的摩擦发电机,所述摩擦发电机进一步包括居间电极层,所述居间电极层设置在第一聚合物材料层和第二聚合物材料层之间。 [0015] The foregoing friction generator, said generator further comprises a friction intervening electrode layers, said intervening layer is disposed between the first electrode material layer and the second polymeric layer of polymeric material.

[0016] 前述的摩擦发电机,所述居间电极层为金属、金属氧化物、合金层,或图形化金属线-高分子聚合物层叠体,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钥;;合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、铋合金、铟合金、镓合金、钨合金、钥合金、铌合金或钽合金,金属氧化物为铟锡氧化物。 [0016] The foregoing friction generator, the intermediate electrode layer is a metal, a metal oxide, an alloy layer, or a patterned metal wire - polymer stacked body, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, key, or key ;; tungsten alloy is wrong alloys, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloys, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, key alloys, niobium alloys or tantalum alloy, a metal oxide is indium tin oxide.

[0017] 本发明图形化金属线-高分子聚合物层叠体是在高分子聚合物层的一侧表面上通过热压、旋涂、刮涂或者丝网印刷金属、金属粉末或金属浆料,形成图形化金属线,从而制备得到的层叠体。 [0017] The present invention is patterned metal lines - polymer laminate is on the side surface of the polymer layer by hot pressing, spin coating, blade coating or screen printing a metal, a metal powder or a metal paste, forming a patterned metal wire, thereby preparing a laminated body obtained. 金属所用材料为金属或合金,其中,金属是金、银、钼、钯、铝、镍、铜、钛、 铬、硒、铁、猛、钥、鹤或钥;;合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、 镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 Metal material is a metal or alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, selenium, iron, fierce, key, key ;; crane or alloy is wrong alloy, titanium , magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys. 本发明金属浆料包括粘合剂、金属粉末、稀释剂等。 Metal slurry of the present invention include binders, metal powders, such as thinner. 粘合剂和稀释剂均为制成金属浆料的常规成分。 Binder and diluent are made of conventional component metal slurry. 这里的图形化是能够导通的图形化,例如井字状结构、菱形状结构、Z字结构或叉指结构。 Here it is capable of conducting graphic graphical, such as tic-tac-like structure, diamond-shaped structure, Z word structure or interdigital structure.

[0018] 前述的摩擦发电机,第一聚合物材料层和居间电极层相对设置的两个面中的至少一个面上,和/或第二聚合物材料层和居间电极层相对设置的两个面中的至少一个面上设置微纳凹凸结构,所述微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构。 [0018] The foregoing friction generators, the two faces of the first polymeric material layer and the intervening layer opposite electrode disposed at least one surface, and / or the second layer of polymeric material and intervening two oppositely disposed electrode layer faces at least one surface uneven structure set up micro-nano, micro and nano convex structure of the bump height of 200nm-100μm bump micro and nano structures.

[0019] 前述的摩擦发电机,第一电极层和第二电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒; 合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、 镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0019] The foregoing friction generator, a first electrode layer and the second electrode layer is indium tin oxide material, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum , nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloy is wrong alloys, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloys, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.

[0020] 前述的摩擦发电机,以重量份计,所述半导体复合材料包括金属颗粒1-50份,和聚合物基底材料30-99份。 [0020] The foregoing friction generators, in parts by weight, the semiconductor composite metal particles comprising 1 to 50 parts, and 30-99 parts of polymer base material.

[0021] 前述的摩擦发电机,所述半导体复合材料包括金属颗粒1-10份,和聚合物基底材料90-99份。 [0021] The foregoing friction generator, the semiconductor composite material comprises 1-10 parts metal particles, and the polymer base material 90-99 parts.

[0022] 前述的摩擦发电机,所述聚合物基底材料是聚二甲基硅氧烷、聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯。 [0022] The foregoing friction generator, the polymer base material is a polydimethylsiloxane, polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride.

[0023]前述的摩擦发电机,所述金属颗粒是银、铜、金、铝、钨、镍、铁中的至少一种,其体积粒径在1_1〇〇ym。 [0023] The foregoing friction generator, the metallic particles are silver, at least one of copper, gold, aluminum, tungsten, nickel, iron, and its volume particle diameter in 1_1〇〇ym.

[0024] 前述的摩擦发电机,所述金属颗粒是经过改性剂表面改性的金属颗粒,金属颗粒与改性剂的重量比为1-50 :1。 [0024] The foregoing friction generator, through the weight of the metal particles are metal particles surface-modified modifier, metallic particles with a modifier ratio 1-50: 1.

[0025] 前述的摩擦发电机,所述金属颗粒与改性剂的重量比为1-30 :1。 [0025] The foregoing friction generator, the weight of the metal particles with a modifier ratio to 30: 1.

[0026] 前述的摩擦发电机,所述改性剂是聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵、月桂酸钠、油酸钠、十二烷基硫酸钠、Y-氯丙基三氯硅烷、Y-氯丙基二甲氧基娃烧、Y_氣丙基甲基-甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二甲氧基硅烷、Y-(甲基丙烯酰氧基)丙基三甲氧基硅烷、β- (3,4环氧环己基)乙基三甲氧基硅烷、 Y-缩水甘油醚基丙基三甲氧基硅烷、Y-巯丙基三甲氧基硅烷、N-β-(氨乙基)-Υ -氨丙基二甲氧基娃烧、Y-脈基丙基二乙氧基娃烧、Y- (3, 2环氧丙氧基)甲基二甲氧基娃烧、 Y-疏丙基二乙氧基娃烧、Y-(乙二胺基)丙基二甲氧基娃烧、Y-氛丙基二乙氧基娃烧、 双-[3_(二乙氧基)娃丙基四硫化物、二乙稀二胺基丙基二甲氧基娃烧、γ-乙二胺基二乙氧基娃烧、A-(乙二胺基)甲基二乙氧基娃烧、苯胺甲基二乙氧基娃烧、苯胺甲基二甲氧基娃烷、双(3-三乙氧基甲硅烷基丙基)四硫化碳、环己基甲基二甲氧基硅烷、钛酸四正丁酯、四异丙氧基钛、2-乙基-1-己醇钛、钛酸四正丙酯、聚钛酸丁酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、 异丙基三(十二烷基苯磺酰基)钛酸酯、三硬脂酸钛酸异丙酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛基焦磷酸酰氧基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、双(乙酰丙酮基)(二异丙基)钛酸酯、双(乙酰丙酮基)(异丁氧基异丙氧基)钛酸酯、双(乙酰丙酮基)(乙氧基异丙氧基)钛酸酯、二(三乙醇胺)钛酸二异丙酯、2,2',2"_氮基三乙基钛酸酯、双(乙酰乙酸乙酯)钛酸二异丁酯中的至少一种。 [0026] The foregoing friction generator, said modifier is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, sodium laurate, oleate, sodium lauryl sulfate, Y- chloropropyl trichlorosilane, Y- chloropropyl dimethoxy baby burn, Y_ gas methylcellulose - methoxy baby burn, ethylene bis-ethoxy baby burning, ethylene dimethoxy silane, Y- (methacryloxy) propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, Y- glycidyl ether trimethoxy silane, Y- mercapto propyl trimethoxy silane, N-β- (aminoethyl) -Υ - aminopropyl dimethoxy baby burn, Y- pulse diethoxy propyl based baby burn, Y- (3, 2 epoxypropoxy) methyldimethoxy baby burn, Y- sparse propyl diethoxy baby burn, Y- (ethylene diamine) propyl-dimethoxyphenyl based baby burn, Y- atmosphere propyl diethoxy baby burn, double - [3_ (diethoxy) propyl tetrasulfide baby, two ethylene diamino propyldimethoxysilane baby burn, γ- ethylenediamino diethoxy baby burn, A- (ethylene diamine-yl) methyl diethoxy baby burn baby burn diethoxy methyl aniline, aniline methyldimethoxy baby, bis ( 3- triethoxysilyl propyl) tetrasulfide carbon, cyclohexyl methyl dimethoxy silane, tetra-n-butyl titanate, titanium tetraisopropoxide, titanium 2-ethyl-1-hexanol , tetra-n-propyl, poly butyl titanate, isopropyl dioleate acyloxy group (acyloxy dioctyl phosphate) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanium ester, isopropyl tri oleic acyloxy titanate, isopropyl tri (dodecylbenzene sulfonyl) titanate, isopropyl titanate tristearate, isopropyl tri (dioctyl acyloxy group pyrophosphate) titanate, bis (dioctyl pyrophosphate acyloxy) ethylene titanate, tetraisopropyl-bis (acyloxy octyl phosphate) titanate, bis (acetyl- Acetone-yl) (diisopropyl) titanate, bis (acetylacetonato) (isobutoxy isopropoxy) titanate, bis (acetylacetonato) (ethoxy isopropoxy) titanate esters, bis (triethanolamine) titanate, diisopropyl 2,2 ', 2 "_ nitrilotriacetic ethyl titanate, bis (ethylacetoacetate) at least one of diisobutyl titanate.

[0027] 前述的摩擦发电机,所述改性剂是十二烷基硫酸钠。 [0027] The foregoing friction generator, the modifying agent is sodium lauryl sulfate.

[0028] 本发明提供的第二技术方案,一种摩擦发电机,包括层叠设置的第一电极层,第一聚合物材料层,居间薄膜层,第二聚合物材料层和第二电极层,其中,第一聚合物材料层和居间薄膜层中的至少一层,和/或第二聚合物材料层和居间薄膜层中的至少一层所用材料是金属掺杂聚合物的半导体复合材料。 [0028] The second aspect of the present invention provides a friction generator comprising a first electrode layer disposed stacked, a first layer of polymeric material, intermediate film layer, a second layer of polymeric material and a second electrode layer, wherein a first intervening layer of polymeric material and at least one thin film layer, and / or the second layer of polymeric material and intervening at least one thin film layer material used is a metal-doped semiconductor polymer composites.

[0029] 前述的摩擦发电机,以重量份计,所述半导体复合材料包括金属颗粒1-50份,和聚合物基底材料30-99份。 [0029] The foregoing friction generators, in parts by weight, the semiconductor composite metal particles comprising 1 to 50 parts, and 30-99 parts of polymer base material.

[0030] 前述的摩擦发电机,以重量份计,所述半导体复合材料包括金属颗粒1-10份,和聚合物基底材料90-99份。 [0030] The foregoing friction generators, in parts by weight, the semiconductor composite metal particles comprising 1-10 parts, and 90-99 parts of polymer base material.

[0031] 前述的摩擦发电机,所述聚合物基底材料是聚二甲基硅氧烷、聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯。 [0031] The foregoing friction generator, the polymer base material is a polydimethylsiloxane, polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride.

[0032] 前述的摩擦发电机,所述金属颗粒是银、铜、金、铝、钨、镍、铁中的至少一种,其体积粒径在l_l〇〇ym。 [0032] The foregoing friction generator, the metallic particles are silver, at least one of copper, gold, aluminum, tungsten, nickel, iron, and its volume particle diameter in l_l〇〇ym.

[0033] 前述的摩擦发电机,所述金属颗粒是经过改性剂表面改性的金属颗粒,金属颗粒与改性剂的重量比为1-50 :1。 [0033] The foregoing friction generator, through the weight of the metal particles are metal particles surface-modified modifier, metallic particles with a modifier ratio 1-50: 1.

[0034] 前述的摩擦发电机,所述金属颗粒与改性剂的重量比为1-30 :1。 [0034] The foregoing friction generator, the weight of the metal particles with a modifier ratio to 30: 1.

[0035] 前述的摩擦发电机,所述改性剂是聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵、月桂酸钠、油酸钠、十二烷基硫酸钠、Y-氯丙基三氯硅烷、Y-氯丙基二甲氧基娃烧、Y_氣丙基甲基-甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二甲氧基硅烷、Y-(甲基丙烯酰氧基)丙基三甲氧基硅烷、β- (3,4环氧环己基)乙基三甲氧基硅烷、 Y-缩水甘油醚基丙基三甲氧基硅烷、Y-巯丙基三甲氧基硅烷、N-β-(氨乙基)-Υ -氨丙基二甲氧基娃烧、Y-脈基丙基二乙氧基娃烧、Y- (3,2环氧丙氧基)甲基二甲氧基娃烧、 Y-疏丙基二乙氧基娃烧、Y-(乙二胺基)丙基二甲氧基娃烧、Y-氛丙基二乙氧基娃烧、 双-[3_(二乙氧基)娃丙基四硫化物、二乙稀二胺基丙基二甲氧基娃烧、γ-乙二胺基二乙氧基娃烧、A-(乙二胺基)甲基二乙氧基娃烧、苯胺甲基二乙氧基娃烧、苯胺甲基二甲氧基娃烷、双(3-三乙氧基甲硅烷基丙基)四硫化碳、环己基甲基二甲氧基硅烷、钛酸四正丁酯、四异丙氧基钛、2-乙基-1-己醇钛、钛酸四正丙酯、聚钛酸丁酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、 异丙基三(十二烷基苯磺酰基)钛酸酯、三硬脂酸钛酸异丙酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛基焦磷酸酰氧基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、双(乙酰丙酮基)(二异丙基)钛酸酯、双(乙酰丙酮基)(异丁氧基异丙氧基)钛酸酯、双(乙酰丙酮基)(乙氧基异丙氧基)钛酸酯、二(三乙醇胺)钛酸二异丙酯、2, 2',2"-氮基三乙基钛酸酯、双(乙酰乙酸乙酯)钛酸二异丁酯中的至少一种。 [0035] The foregoing friction generator, said modifier is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, sodium laurate, oleate, sodium lauryl sulfate, Y- chloropropyl trichlorosilane, Y- chloropropyl dimethoxy baby burn, Y_ gas methylcellulose - methoxy baby burn, ethylene bis-ethoxy baby burning, ethylene dimethoxy silane, Y- (methacryloxy) propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, Y- glycidyl ether trimethoxy silane, Y- mercapto propyl trimethoxy silane, N-β- (aminoethyl) -Υ - aminopropyl dimethoxy baby burn, Y- pulse diethoxy propyl based baby burn, Y- (3,2-epoxypropoxy) methyldimethoxy baby burn, Y- sparse propyl diethoxy baby burn, Y- (ethylene diamine) propyl dimethoxyethane based baby burn, Y- atmosphere propyl diethoxy baby burn, double - [3_ (diethoxy) propyl tetrasulfide baby, two ethylene diamino propyldimethoxysilane baby burn, γ- ethylenediamino diethoxy baby burn, A- (ethylene diamine-yl) methyl diethoxy baby burn baby burn diethoxy methyl aniline, aniline methyldimethoxy baby, bis ( 3- triethoxysilyl propyl) tetrasulfide carbon, cyclohexyl methyl dimethoxy silane, tetra-n-butyl titanate, titanium tetraisopropoxide, titanium 2-ethyl-1-hexanol , tetra-n-propyl, poly butyl titanate, isopropyl dioleate acyloxy group (acyloxy dioctyl phosphate) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanium ester, isopropyl tri oleic acyloxy titanate, isopropyl tri (dodecylbenzene sulfonyl) titanate, isopropyl titanate tristearate, isopropyl tri (dioctyl acyloxy group pyrophosphate) titanate, bis (dioctyl pyrophosphate acyloxy) ethylene titanate, tetraisopropyl-bis (acyloxy octyl phosphate) titanate, bis (acetyl- Acetone-yl) (diisopropyl) titanate, bis (acetylacetonato) (isobutoxy isopropoxy) titanate, bis (acetylacetonato) (ethoxy isopropoxy) titanate esters, bis (triethanolamine) titanate, di-iso-propyl, 2, 2 ', 2 "- nitrilotriacetic ethyl titanate, bis (ethylacetoacetate) at least one of diisobutyl titanate.

[0036] 前述的摩擦发电机,所述改性剂是十二烷基硫酸钠。 [0036] The foregoing friction generator, the modifying agent is sodium lauryl sulfate.

[0037]前述的摩擦发电机,第一聚合物材料层和居间薄膜层相对设置的两个面中的至少一个面上设置微纳凹凸结构,和/或第二聚合物材料层和居间薄膜层相对设置的两个面中的至少一个面上设置微纳凹凸结构; [0037] The foregoing friction generator, the two faces of the first polymeric material layer and the intervening film layer disposed opposite at least one surface of convex structure set up micro-nano, and / or the second layer of polymeric material and intervening film layer two oppositely disposed surfaces of at least one surface of convex structure set up micro-nano;

[0038]所述第一聚合物材料层,和/或居间薄膜层,和/或第二聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100ym的微纳凹凸结构。 Micronanoelectronic uneven structure provided on [0038] the first layer of polymeric material, and / or intervening film layer, and / or the second layer of polymeric material surface is convex micro-nano convex structure height of 200nm-100ym.

[0039]前述的摩擦发电机,第一电极层和第二电极层所用材料是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒; 合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、 镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0039] The foregoing friction generator, a first electrode layer and the second electrode layer is indium tin oxide material, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum , nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloy is wrong alloys, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloys, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.

[0040]前述的摩擦发电机,当第一聚合物材料层,或居间薄膜层,或第二聚合物材料层不采用半导体复合材料时,其所用材料选自聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、 乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、 再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 [0040] The foregoing friction generator, when the first layer of polymeric material, or intervening film layer, a second layer of polymeric material or semiconductor composite is not used, its material is selected from polyimide film, aniline-formaldehyde resin films, polyoxymethylene film, ethylcellulose film, a polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, cellulose film, cellulose acetate film, polyethylene adipate film , poly diallyl phthalate film, cellulose film sponge, renewable sponge film, a polyurethane elastomer film, styrene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate ester film, polyvinyl alcohol film, polyisobutylene film, polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film , natural rubber film, polyacrylonitrile film, acrylonitrile-vinyl chloride copolymer film of any one.

[0041] 本发明掺杂金属颗粒到绝缘聚合物中,降低聚合物的电阻率,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平。 [0041] The present invention is doped metal particles into the insulating polymer, the lower the resistivity of the polymer, so that the volume resistivity between horizontal metal volume resistivity and volume resistivity of insulating material between. 金属掺杂聚合物的半导体复合材料既具备了金属颗粒的功能特性如导电性,也具有聚合物材料优良的机械性能和可加工性。 Metal-doped polymer semiconductor composites only has the features of the metal particles, such as conductivity, also has a polymer material excellent mechanical properties and processability. 在摩擦发电机中使用该半导体复合物材料可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 The use of composite materials in the semiconductor generator can effectively reduce the friction resistance generator work, within a certain range can increase the friction of the generator load capacity.

附图说明 Brief Description

[0042] 图1为本发明摩擦发电机一种具体实施方式的立体结构示意图。 [0042] Figure 1 is a perspective view of the invention the friction generator schematic structural view of specific embodiments.

[0043] 图2为本发明图1摩擦发电机的剖面结构示意图。 [0043] FIG. 2 is a schematic cross-sectional structure diagram in Figure 1 friction generator.

[0044] 图3为本发明摩擦发电机另一种具体实施方式的立体结构示意图。 [0044] FIG. 3 of the present invention friction generating another schematic view of a specific embodiment.

[0045] 图4为本发明图3摩擦发电机的剖面结构示意图。 [0045] FIG. 4 a schematic cross-sectional structure of the present invention FIG. 3 friction generator.

[0046] 图5为本发明摩擦发电机另一种具体实施方式的立体结构示意图。 [0046] Figure 5 is another perspective view of the invention the friction generator schematic structural view of a specific embodiment.

[0047] 图6为本发明图5摩擦发电机的立体结构示意图。 [0047] FIG. 6 shows a schematic view of the present invention Figure 5 friction generator.

[0048] 图7为本发明摩擦发电机另一种具体实施方式的立体结构示意图。 [0048] Figure 7 is another perspective view of the invention the friction generator schematic structural view of a specific embodiment.

[0049] 图8为本发明图7摩擦发电机的立体结构示意图。 [0049] FIG. 8 shows a schematic view of the present invention Figure 7 friction generator.

[0050] 图9为采用Cu掺杂聚合物半导体复合材料为聚合物材料层的摩擦发电机的开路电压输出值。 [0050] FIG. 9 is the use of open-circuit voltage output value of Cu-doped polymer semiconductor composite polymer material layer friction generator.

[0051] 图10为采用Cu掺杂聚合物半导体复合材料为聚合物材料层的摩擦发电机的IMΩ 负载电压输出值。 [0051] FIG. 10 IMΩ output value of the load voltage using Cu doped semiconductor composite polymer material is a polymer material layer, the friction of the generator.

[0052] 图11为常规聚合物材料层的摩擦发电机的开路电压输出值。 [0052] FIG. 11 is a conventional open-circuit voltage value of the output layer of polymeric material friction generator.

[0053] 图12为常规聚合物材料层的摩擦发电机的1ΜΩ负载电压输出值。 [0053] FIG. 12 is the load voltage output 1ΜΩ conventional friction layer of polymeric material generator.

具体实施方式 DETAILED DESCRIPTION

[0054] 为充分了解本发明之目的、特征及功效,借由下述具体的实施方式,对本发明做详细说明。 [0054] In order to fully understand the purpose of the present invention, the characteristics and effects, by the following specific embodiments of the present invention will be described in detail.

[0055] 本发明提供了一种金属掺杂聚合物的半导体复合材料,以重量份计,金属颗粒1-50份,和聚合物基底材料30-99份。 [0055] The present invention provides a metal-doped semiconductor polymer composites, in parts by weight, 1-50 parts of metal particles, and 30-99 parts of polymer base material. 优选金属颗粒1-10份,和聚合物基底材料90-99份。 Preferably 1 to 10 parts metallic particles, and 90-99 parts of polymer substrate material.

[0056] 本发明所用聚合物基底材料是聚二甲基硅氧烷、聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯。 [0056] The present invention is a polymer base material polydimethylsiloxane, polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride. 将上述材料溶解于二甲基乙酰胺(DMA),会形成液态溶液。 The above material is dissolved in dimethylacetamide (DMA), will form a liquid solution. 聚二甲基硅氧烷本身即为液态,不需要溶解于二甲基乙酰胺(DMA)。 Dimethicone itself is liquid, it does not require dissolved in dimethylacetamide (DMA).

[0057] 本发明所用金属颗粒是银、铜、金、铝、钨、镍、铁中的至少一种,其体积粒径在1-100μm。 [0057] The present invention is a silver metal particles, at least one of copper, gold, aluminum, tungsten, nickel, iron, and its volume particle size in 1-100μm. 优选的,所述金属颗粒是经过改性剂表面改性的金属颗粒,金属颗粒与改性剂的重量比为1-50 :1,优选的,所述金属颗粒与改性剂的重量比为1-30:1。 Preferably, the metal particles are surface-modified metal particles modifier, the weight ratio of the metal particles and the modifying agent is 1-50: 1, preferably, the weight of the metal particles and the ratio of modifier 1-30: 1.

[0058] 上述改性剂可以是聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵、月桂酸钠、油酸钠、十二烷基硫酸钠、Y-氯丙基三氯硅烷、Y-氯丙基三甲氧基硅烧、Y-氣丙基甲基-甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二甲氧基娃烧、Y-(甲基丙烯酰氧基)丙基三甲氧基硅烷、β- (3,4环氧环己基)乙基三甲氧基硅烷、γ-缩水甘油醚基丙基三甲氧基硅烷、Υ -巯丙基三甲氧基硅烷、N-β-(氨乙基)-γ-氨丙基三甲氧基硅烧、Y_脈基丙基二乙氧基娃烧、Y_ (3, 2环氧丙氧基)甲基二甲氧基娃烧、γ-疏丙基二乙氧基娃烧、Y-(乙二胺基)丙基二甲氧基娃烧、Y-氛丙基二乙氧基娃烧、双-[3_ (二乙氧基)娃丙基四硫化物、_乙稀二胺基丙基二甲氧基娃烧、Y_乙_胺基二乙氧基娃烧、A-(乙二胺基)甲基二乙氧基娃烧、苯胺甲基二乙氧基娃烧、苯胺甲基二甲氧基娃烧、双(3-二乙氧基甲硅烷基丙基)四硫化碳、环己基甲基二甲氧基硅烷、钛酸四正丁酯、四异丙氧基钛、2-乙基-1-己醇钛、钛酸四正丙酯、聚钛酸丁酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯、三硬脂酸钛酸异丙酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛基焦磷酸酰氧基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、双(乙酰丙酮基)(二异丙基)钛酸酯、双(乙酰丙酮基)(异丁氧基异丙氧基)钛酸酯、双(乙酰丙酮基)(乙氧基异丙氧基)钛酸酯、二(三乙醇胺)钛酸二异丙酯、2,2',2"_氮基三乙基钛酸酯、双(乙酰乙酸乙酯)钛酸二异丁酯中的至少一种。优选的改性剂是十二烷基硫酸钠 [0058] The above-mentioned modifier may be polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, sodium laurate, sodium oleate, sodium lauryl sulfate , Y- chloropropyl trichlorosilane, Y- chloropropyl trimethoxysilane burn, Y- gas methylcellulose - methoxy baby burn baby burn diethoxy ethylene group, ethylene group dimethyl group baby burn, Y- (methacryloxy) propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, γ- glycidyl propyl trimethoxy silane, Υ - mercaptopropyl trimethoxysilane, N-β- (aminoethyl) -γ- aminopropyl trimethoxysilane burn, Y_ pulse propyl diethoxy baby burn, Y_ (3 2 epoxypropoxy) methyldimethoxy baby burn, γ- sparse propyl diethoxy baby burn, Y- (ethylene diamine) propyl dimethoxy baby burn, Y- atmosphere propionate group diethoxy baby burn, double - [3_ (diethoxy) propyl tetrasulfide baby, _ ethylene diamino propyldimethoxysilane baby burn, Y_ _ amino ethyl diethoxy baby burn, A- (ethylene diamine-yl) methyl diethoxy baby burn baby burn diethoxy methyl aniline, aniline methyldimethoxy baby burn, bis (3-triethoxysilyl yl-propyl) tetrasulfide carbon, cyclohexyl methyl dimethoxy silane, tetra-n-butyl titanate, titanium tetraisopropoxide, titanium 2-ethyl-1-hexanol, tetra-n-propyl, poly butyl titanate, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tri oil acyloxy acid titanate, isopropyl tri (dodecyl benzene sulfonyl) titanate, isopropyl titanate tristearate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanium esters, bis (dioctyl pyrophosphate acyloxy) ethylene titanate, tetraisopropyl-bis (octyl phosphoric acyloxy) titanate, bis (acetylacetonate) (diisopropyl ) titanate, bis (acetylacetonato) (isobutoxy isopropoxy) titanate, bis (acetylacetonato) (ethoxy isopropoxy) titanate, bis (triethanolamine) titanium di-iso-propyl, 2,2 ', 2 "_ nitrilotriacetic ethyl titanate, bis (ethylacetoacetate) at least one of diisobutyl titanate preferred modifier is twelve alkyl sulfate

[0059] 下面详细说明一下上述半导体复合材料的制备方法。 [0059] The following detailed descriptions of the above preparation method of the semiconductor composites. 该方法包括:选择性步骤(1)对金属颗粒进行改性处理,具体的采用改进剂对金属颗粒进行表面处理,得到经过改性剂表面改性的金属颗粒。 The method comprises: optional step (1) modification of metal particles, the specific use of modifiers of the metal particles subjected to surface treatment to obtain surface-modified metal particles modifier. 本发明所用表面处理方法为常规金属颗粒表面处理方法。 The surface treatment method of the present invention is used as a conventional metal particle surface treatment.

[0060] (2)准备聚合物基底材料液态溶液。 [0060] (2) preparing a liquid solution of polymer base material. 具体的,将聚偏氟乙烯、聚甲基丙烯酸甲酯或聚氯乙烯溶于二甲基乙酰胺(DMA)形成液态溶液。 Specifically, the polyvinylidene fluoride, polymethyl methacrylate or polyvinyl chloride dissolved in dimethylacetamide (DMA) forming a liquid solution. 聚二甲基硅氧烷本身就是液态的,可以直接应用于第二步骤。 Dimethicone itself is liquid, it can be directly applied to the second step.

[0061] (3)将金属颗粒加入到步骤(2)所得液态溶液混合均匀。 [0061] (3) the metal particles are added to the step (2) mixing the resulting homogeneous liquid solution. 当聚合物采用聚二甲基硅氧烷时,需要采用聚二甲基硅氧烷和固化剂(硫化剂,通常比例为10 :1),所用固化剂为市售常规固化剂,例如道康宁184。 When using polydimethylsiloxane polymers, they require the use of polydimethylsiloxane and a curing agent (vulcanizing agent, generally a ratio of 10: 1), the curing agent is the commercially available conventional curing agents, such as Dow Corning 184 .

[0062] (4)将步骤(3)所得液体涂膜、烘干,得到至少一个侧表面设置微纳凹凸结构或两个侧表面均具有微纳凹凸结构的薄膜。 [0062] (4) The step (3) the resulting liquid coating and drying, to obtain at least one side surface of micro-nano uneven structure or both side surfaces have uneven film micro and nano structures.

[0063]本发明采用常规丝网印刷、涂覆、旋涂等方法在硅模板上制备具有凹凸结构的薄膜。 [0063] The present invention uses a conventional screen printing, coating, spin coating method for preparing a film on a silicon template uneven structure. 本发明采用机械搅拌的方式(球磨、磁力搅拌、搅拌杆搅拌)将物料混合均匀。 The present invention employs a mechanically stirred mode (milling, magnetic stirring, stirring rod stirring) the material is mixed.

[0064]本发明半导体复合材料应用在摩擦发电机中。 [0064] The present invention is applied to semiconductor composite friction generator. 下面详细说明应用半导体复合材料的摩擦发电机的结构。 The following detailed description of the structure of the application semiconductor composite friction generator.

[0065]图1和图2所示是本发明一种具体实施方式的摩擦发电机1。 Shown in [0065] FIG. 1 and FIG. 2 is a specific embodiment of the present invention is a friction generator 1. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 其中,第一聚合物材料层12所用材料是上述的金属掺杂聚合物的半导体复合材料层,其厚度为100μm-500μm。 Wherein a first layer of polymeric material 12 is a semiconductor composite material layer of the above-described metal-doped polymer, a thickness of 100μm-500μm.

[0066] 第一聚合物材料层12和第二电极层13相对设置的两个面中的至少一个面上设置微纳凹凸结构14 (图2仅示出第一聚合物材料层12上的微纳凹凸结构),所述第一聚合物材料层表面上设置的微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构;所述第二电极层表面上设置的微纳凹凸结构为凸起高度200nm-100ym的微纳凹凸结构。 [0066] The first polymeric material layer 12 and at least one surface of two opposite surfaces of the second electrode layer 13 disposed on the settings in micro-nano convex structure 14 (FIG. 2 shows only 12 micro-material layer of the first polymer Carolina convex structure), micro-nano uneven structure disposed on the first layer of polymeric material surface protrusion height of 200nm-100μm micro-nano convex structure; Micronanoelectronic uneven structure provided on the surface of the second electrode layer is convex From the height of 200nm-100ym of micro-nano convex structure.

[0067] 该实施方式中,第一电极层11对所用材料没有特殊规定,能够形成导电层的材料都在本发明的保护范围之内,例如是铟锡氧化物、石墨烯、银纳米线膜、金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、钛合金、镁合金、 铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、 鹤合金、钥合金、银合金或钽合金。 [0067] In this embodiment, the first electrode layer 11 pairs otherwise specified the materials used, the material of the conductive layer can be formed are within the scope of the present invention, for example, indium tin oxide, graphene, silver nanowire film , metal or alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloys are aluminum, titanium, magnesium alloys, beryllium alloy, copper alloy, zinc alloy, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys.

[0068] 该实施方式中,第二电极层13所用材料可以是金属或合金,其中金属可以是金、 银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金可以是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0068] In this embodiment, the second electrode layer 13 may be a metal material or an alloy, wherein the metal may be gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole , tungsten or vanadium; alloys may be aluminum, titanium, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, Crane alloy, key alloy, silver alloy or tantalum alloys. 第二电极层13的厚度优选100μm-500μm,更优选200μm。 Thickness of the second electrode layer 13 is preferably 100μm-500μm, more preferably 200μm.

[0069] 当本发明该实施方式的摩擦发电机的各层向下弯曲时,摩擦发电机中的第一聚合物材料层12与第二电极层13表面相互摩擦产生静电荷,静电荷的产生会使第一聚合物材料层12与第二电极层13之间的电容发生改变,从而导致第一聚合物材料层12与第二电极层13之间出现电势差。 [0069] When the layers of the embodiment of the present invention a friction generator is bent downward, the friction in the generator layer 12 and a first polymeric material surface of the second electrode layer 13 to generate friction between an electrostatic charge, electrostatic charge generating make a first layer of polymeric material 12 and the capacitance between the second electrode layer 13 changes, thereby resulting in a potential difference between the first polymer material 13 layer 12 and the second electrode layer. 由于第一聚合物材料层12与第二电极层13之间电势差的存在,自由电子将通过外电路由电势低的一侧流向电势高的一侧,从而在外电路中形成电流。 13 since the potential difference between a first layer of polymeric material 12 and the second electrode layer is present, the high side of the free electrons through the potential foreign routed low potential side of the flow, thereby forming the outer circuit current. 当本发明的摩擦发电机的各层恢复到原来状态时,这时形成在第一聚合物材料层12与第二电极层13之间的内电势消失,此时已平衡的第一聚合物材料层12与第二电极层13之间将再次产生反向的电势差,则自由电子通过外电路形成反向电流。 When the generator of the present invention, the friction layers restored to its original state, then formed in a first layer of polymeric material 12 and the inner electric potential between the second electrode layer 13 disappears, and the balance of the first polymeric material has layer 12 and the second electrode layer 13 will again be generated between the reverse potential difference, the free electrons formed reverse current through the external circuit. 通过反复摩擦和恢复,就可以在外电路中形成周期性的交流电信号。 By repeated friction and recovery, it can periodically formed in the outer circuit alternating current signal. 本发明该实施方式中,采用金属掺杂聚合物的半导体复合材料作为第一聚合物材料层12,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平,因而可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 The embodiment of the present invention, the use of metal-doped polymer composite material as the semiconductor layer of a first polymeric material 12, so that the volume resistivity and the volume resistivity between metal levels between the volume resistivity of the insulating material, which can effectively reduce the internal resistance of the generator is working, within a certain range can increase the friction of the generator load capacity.

[0070] 图3和图4所示是本发明另一种具体实施方式的摩擦发电机2。 [0070] Figure 3 and Figure 4 shows the present invention, another specific embodiment of the friction generator 2. 该摩擦发电机2 包括层叠设置的第一电极层21,第一聚合物材料层22,第二聚合物材料层23和第二电极层24,其中,第一聚合物材料层22和第二聚合物材料层23中的至少一层所用材料是上述的金属掺杂聚合物的半导体复合材料层,其厚度为100μm-500μm。 The friction generator 2 comprises a first electrode layer 21 disposed stacked, a first layer of polymeric material 22, a second layer of polymeric material 23 and the second electrode layer 24, wherein the first polymeric material and a second polymeric layer 22 material layer 23 at least one layer of semiconductor material used is a composite layer of the metal-doped polymer, a thickness of 100μm-500μm.

[0071] 第一聚合物材料层22和第二聚合物材料层23相对设置的两个面中的至少一个面上设置微纳凹凸结构25 (图4仅示出第一聚合物材料层22上的微纳凹凸结构),该微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构。 [0071] provided at least one surface of the two micro-nano convex structure 25 side of the first layer of polymeric material 22 and the second layer of polymeric material 23 disposed in the opposite (FIG. 4 shows only a first layer of polymeric material 22 The micro-nano uneven structure), the micro-nano convex structure 200nm-100μm bump height of micro-nano convex structure.

[0072] 在该实施方式中,第一电极层21和第二电极层24对所用材料没有特殊规定,能够形成导电层的材料都在本发明的保护范围之内,例如是铟锡氧化物、石墨烯、银纳米线膜、 金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0072] In this embodiment, the first electrode layer 21 and the second electrode layer 24 pairs otherwise specified the materials used, the material of the conductive layer can be formed are within the scope of the present invention, for example, indium tin oxide, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloy is an aluminum alloy, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys .

[0073] 第一聚合物材料层22和第二聚合物材料层23中的至少一层所用材料是上述半导体复合材料层。 [0073] The first polymeric material layer 22 and the second layer of polymeric material 23 in at least one of the semiconductor material used is a composite material layer. 当第一聚合物材料层22或第二聚合物材料层23不采用半导体复合材料层时,其所用材料选自聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 When the first layer of polymeric material 22 or the second layer of polymeric material 23 without using a semiconductor composite material layer, its material is selected from polyimide film, aniline-formaldehyde resin film, a polyoxymethylene film, ethylcellulose film, polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, cellulose film, cellulose acetate film, polyethylene adipate film, polyethylene film diallyl phthalate, cellulose sponge film, regenerated sponge film, a polyurethane elastomer film, styrene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, a polyvinyl alcohol film, polyisobutylene films , polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film, a natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride copolymer film of any one. 此时,第一聚合物材料层22或第二聚合物材料层23厚度是100μm-500μm。 In this case, the thickness of the first polymer material layer 23 or second layer of polymeric material 22 is 100μm-500μm.

[0074] 当本发明该实施方式的摩擦发电机的各层向下弯曲时,摩擦发电机中的第一聚合物材料层22与第二聚合物材料层23表面相互摩擦产生静电荷,静电荷的产生会使第一聚合物材料层22与第二聚合物材料层23之间的电容发生改变,从而导致第一电极层21和第二电极层24之间出现电势差。 [0074] When the layers of the embodiment of the present invention is bent downward frictional generator, the generator of the first friction layer of polymeric material 22 and the second layer of polymeric material 23 from each other friction surface electrostatic charge, electrostatic charge It will produce a first layer of polymeric material 22 and the second layer of polymeric material 23 between the capacitance change occurs, thus resulting in a potential difference between the first electrode layer 21 and the second electrode layer 24. 由于第一电极层21和第二电极层24之间电势差的存在,自由电子将通过外电路由电势低的一侧流向电势高的一侧,从而在外电路中形成电流。 Because of between 21 and the second electrode layer 24 a potential difference between the first electrode layer is present, free electrons will be routed through the foreign potential of the low potential side of the high side of the flow direction, thereby forming the outer circuit current. 当本发明的摩擦发电机的各层恢复到原来状态时,这时形成在第一电极层21和第二电极层24 之间的内电势消失,此时已平衡的第一电极层21和第二电极层24之间将再次产生反向的电势差,则自由电子通过外电路形成反向电流。 The first electrode layer when the generator of the present invention, the friction layers restored to its original state, then formed in the potential disappearance of 21 and the second electrode layer 24 between the first electrode layer, this time has been balanced and 21 The second electrode layer 24 is again generated between a reverse potential difference, the free electrons formed reverse current through the external circuit. 通过反复摩擦和恢复,就可以在外电路中形成周期性的交流电信号。 By repeated friction and recovery, it can periodically formed in the outer circuit alternating current signal. 本发明该实施方式中,采用金属掺杂聚合物的半导体复合材料作为第一聚合物材料层22和/或第二聚合物材料层23,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平,因而可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 The embodiment of the present invention, the use of metal-doped polymer composite material as the semiconductor layer of a first polymeric material 22 and / or the second layer of polymeric material 23, so that the volume resistivity and the volume resistivity of the insulating material between the metal level between the volume resistivity, which can effectively reduce the internal resistance of the generator is working, within a certain range can increase the friction of the generator load capacity.

[0075] 图5和图6所示是本发明又一种具体实施方式的摩擦发电机3。 [0075] FIG. 5 and FIG. 6 of the present invention is yet another specific embodiment of the friction generator 3. 该摩擦发电机3 包括第一电极层31,第一聚合物材料层32,居间薄膜层33,第二聚合物材料层34和第二电极层35,其中,第一聚合物材料层32和居间薄膜层33中的至少一层,和/或第二聚合物材料层34和居间薄膜层33中的至少一层所用材料是上述的金属掺杂聚合物的半导体复合材料层,其厚度为100μm-500μm。 The friction generator 3 comprises a first electrode layer 31, a first layer of polymeric material 32, intermediate film layer 33, a second layer of polymeric material 34 and the second electrode layer 35, wherein a first layer of polymeric material 32 and the intervening the thin film layer 33 at least one layer, at least one used and / or the second layer of polymeric material 34 and the intervening film layer 33 or the material is a semiconductor composite material layer above the metal-doped polymer, having a thickness of 100μm- 500μm.

[0076] 第一聚合物材料层32和居间薄膜层33相对设置的两个面中的至少一个面上设置微纳凹凸结构(图未示),和/或第二聚合物材料层34和居间薄膜层33相对设置的两个面中的至少一个面上设置微纳凹凸结构(图未示); [0076] The first polymeric material layer 32 and both sides of the intervening film layer 33 disposed opposite at least one surface of convex structure set up micro-nano (not shown), and / or the second layer of polymeric material 34 and intervening both sides of the thin film layer 33 is oppositely disposed at least one set of micro-nano uneven surface structure (not shown);

[0077] 当第一聚合物材料层32,居间薄膜层33,第二聚合物材料层34表面上设置有微纳凹凸结构时,该微纳凹凸结构为凸起高度200nm-100μm的微纳凹凸结构。 [0077] When the first layer of polymeric material 32, intermediate film layer 33 is provided with a micro-nano convex structure on the surface of the second polymer layer 34, the micro-nano convex structure 200nm-100μm bump height of micro-nano irregularities structure.

[0078] 在该实施方式中,第一电极层31和第二电极层35对所用材料没有特殊规定,能够形成导电层的材料都在本发明的保护范围之内,例如是铟锡氧化物、石墨烯、银纳米线膜、 金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0078] In this embodiment, the first electrode layer 31 and the second electrode layer 35 pairs otherwise specified the materials used, the material of the conductive layer can be formed are within the scope of the present invention, for example, indium tin oxide, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloy is an aluminum alloy, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys .

[0079] 第一聚合物材料层32和居间薄膜层33中的至少一层,和/或第二聚合物材料层34和居间薄膜层33中的至少一层所用材料是半导体复合材料层。 [0079] The first layer of polymeric material 32 and film layers 33 intervening at least one layer, and / or the second layer of polymeric material 34 and the intervening film layer 33, or at least one layer of semiconductor material used is a composite material layer. 当第一聚合物材料层32, 或居间薄膜层33,或第二聚合物材料层34不采用半导体复合材料层时,其所用材料选自聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 When the first layer of polymeric material 32, or intervening film layer 33, or the second layer of polymeric material 34 without using a semiconductor composite material layer, its material is selected from polyimide film, aniline-formaldehyde resin film, a polyoxymethylene film , ethyl cellulose film, a polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, cellulose film, cellulose acetate film, polyethylene adipate film, poly phthalic acid diallyl film, cellulose film sponge, renewable sponge film, a polyurethane elastomer film, styrene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, poly vinyl alcohol film, polyisobutylene film, polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film, a film of natural rubber, polyacrylonitrile film, acrylonitrile-vinyl chloride copolymer film of any one. 此时,第一聚合物材料层32,或居间薄膜层33,或第二聚合物材料层34厚度是100μm-500μm。 In this case, a first layer of polymeric material 32, or 33, or the thickness of the second layer of polymeric material 34 intervening film layer is 100μm-500μm.

[0080] 当本发明该实施方式的摩擦发电机的各层向下弯曲时,摩擦发电机中的第一聚合物材料层32与居间薄膜层33表面,和/或第二聚合物材料层34与居间薄膜层33表面相互摩擦产生静电荷,静电荷的产生会使第一电极层31和第二电极层35之间出现电势差。 [0080] When the layers of the embodiment of the present invention is bent downward friction generator 33 and the intervening film layer surface 32 of the first friction generator layer of polymeric material, and / or the second layer of polymeric material 34 and 33 surface friction between the intervening film layers produce an electrostatic charge, a potential difference occurs between the electrostatic charge generation makes the first electrode layer 31 and the second electrode layer 35. 由于第一电极层31和第二电极层35之间电势差的存在,自由电子将通过外电路由电势低的一侧流向电势高的一侧,从而在外电路中形成电流。 Since the first electrode layer 31 and the second electrode layer 35 in the presence of potential difference, the potential of free electrons will flow to the high potential side low routed through foreign side, thereby forming the outer circuit current. 当本发明的摩擦发电机的各层恢复到原来状态时,这时形成在第一电极层31和第二电极层35之间的内电势消失,此时已平衡的第一电极层31和第二电极层35之间将再次产生反向的电势差,则自由电子通过外电路形成反向电流。 The first electrode layer when the generator of the present invention, the friction layers restored to its original state, then formed in the potential disappearance of 31 and the second electrode layer 35 between the first electrode layer, this time of 31 and balance the second electrode layer 35 will again produce a reverse potential difference, the free electrons formed reverse current through the external circuit. 通过反复摩擦和恢复,就可以在外电路中形成周期性的交流电信号。 By repeated friction and recovery, it can periodically formed in the outer circuit alternating current signal. 本发明该实施方式中,采用金属掺杂聚合物的半导体复合材料作为第一聚合物材料层32,和/或居间薄膜层33,和/或第二聚合物材料层34,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平,因而可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 The embodiment of the present invention, the use of metal-doped polymer composite material as the semiconductor layer of a first polymeric material 32, and / or intervening film layer 33, and / or the second layer of polymeric material 34, so that the volume resistivity between the horizontal metal between the volume resistivity and the volume resistivity of the insulating material, which can effectively reduce the work of the internal resistance of the generator, within a certain range can increase the friction of the generator load capacity.

[0081] 图7和8所示是本发明又一种具体实施方式的摩擦发电机4。 [0081] Figures 7 and 8 of the present invention is shown still another specific embodiment of the friction generator 4. 该摩擦发电机4包括第一电极层41,第一聚合物材料层42,居间电极层43,第二聚合物材料层44和第二电极层45,其中,第一聚合物材料层42和第二聚合物材料层44中的至少一层所用材料是上述的金属掺杂聚合物的半导体复合材料层,其厚度为100μm-500μm。 The friction generator 4 comprises a first electrode layer 41, a first layer of polymeric material 42, intermediate electrode layer 43, a second layer of polymeric material 44 and the second electrode layer 45, wherein a first layer of polymeric material 42 and the first Second layer of polymeric material 44 in at least one of the materials is a semiconductor composite material layer above the metal-doped polymer, a thickness of 100μm-500μm.

[0082] 第一聚合物材料层41和居间电极层43相对设置的两个面中的至少一个面上,和/或第二聚合物材料层44和居间电极层43相对设置的两个面中的至少一个面上设置微纳凹凸结构(图未示),所述微纳凹凸结构为凸起高度200nm-100ym的微纳凹凸结构。 [0082] 41 and the two surfaces of the two opposite faces 43 intervening electrode layers disposed at least one surface, and / or the second layer of polymeric material 44 and the intermediate electrode layer 43 disposed opposite the first layer of polymeric material setting at least one surface micro-nano convex structure (not shown), the micro-nano uneven structure bump height 200nm-100ym of micro-nano convex structure.

[0083] 在该实施方式中,第一电极层41和第二电极层45对所用材料没有特殊规定,能够形成导电层的材料都在本发明的保护范围之内,例如是铟锡氧化物、石墨烯、银纳米线膜、 金属或合金,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 [0083] In this embodiment, the first electrode layer 41 and the second electrode layer 45 pairs otherwise specified the materials used, the material of the conductive layer can be formed are within the scope of the present invention, for example, indium tin oxide, graphene, silver nanowire film, a metal or an alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloy is an aluminum alloy, titanium alloys, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys .

[0084] 所述居间电极层43为金属、金属氧化物、合金层,或图形化金属线-高分子聚合物层叠体,其中金属是金、银、钼、钯、铝、镍、铜、钛、铬、锡、铁、锰、钥、钨或钒;合金是铝合金、 钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、镍合金、铅合金、锡合金、镉合金、秘合金、 铟合金、镓合金、钨合金、钥合金、铌合金或钽合金,金属氧化物为铟锡氧化物。 [0084] The intermediate electrode layer 43 is a metal, a metal oxide, an alloy layer, or a patterned metal wire - polymer stacked body, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium , chromium, tin, iron, manganese, keyhole, tungsten or vanadium; alloys are aluminum, titanium, magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, tungsten alloy, key alloys, niobium alloys or tantalum alloy, a metal oxide is indium tin oxide.

[0085] 本发明图形化金属线-高分子聚合物层叠体是在高分子聚合物层的一侧表面上通过热压、旋涂、刮涂或者丝网印刷金属、金属粉末或金属浆料,形成图形化金属线,从而制备得到的层叠体。 [0085] The present invention is patterned metal lines - polymer laminate is on the side surface of the polymer layer by hot pressing, spin coating, blade coating or screen printing a metal, a metal powder or a metal paste, forming a patterned metal wire, thereby preparing a laminated body obtained. 金属所用材料为金属或合金,其中,金属是金、银、钼、钯、铝、镍、铜、钛、 铬、硒、铁、猛、钥、鹤或钥;;合金是错合金、钛合金、镁合金、铍合金、铜合金、锌合金、猛合金、 镍合金、铅合金、锡合金、镉合金、秘合金、铟合金、镓合金、鹤合金、钥合金、银合金或钽合金。 Metal material is a metal or alloy, wherein the metal is gold, silver, molybdenum, palladium, aluminum, nickel, copper, titanium, chromium, selenium, iron, fierce, key, key ;; crane or alloy is wrong alloy, titanium , magnesium alloys, beryllium alloys, copper alloys, zinc alloys, fierce alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, secret alloy, indium alloy, gallium alloy, alloy crane, key alloy, silver alloy or tantalum alloys. 本发明金属浆料包括粘合剂、金属粉末、稀释剂等。 Metal slurry of the present invention include binders, metal powders, such as thinner. 粘合剂和稀释剂均为制成金属浆料的常规成分。 Binder and diluent are made of conventional component metal slurry. 这里的图形化是能够导通的图形化,例如井字状结构、菱形状结构、Z字结构或叉指结构。 Here it is capable of conducting graphic graphical, such as tic-tac-like structure, diamond-shaped structure, Z word structure or interdigital structure.

[0086] 第一聚合物材料层42和第二聚合物材料层44中的至少一层所用材料是上述半导体复合材料层。 [0086] The first layer of polymeric material 42 and the second polymeric material layer 44 at least one layer of the semiconductor material used is a composite material layer. 当第一聚合物材料层42或第二聚合物材料层44不采用半导体复合材料层时,其所用材料选自聚酰亚胺薄膜、苯胺甲醛树脂薄膜、聚甲醛薄膜、乙基纤维素薄膜、聚酰胺薄膜、三聚氰胺甲醛薄膜、聚乙二醇丁二酸酯薄膜、纤维素薄膜、纤维素乙酸酯薄膜、聚己二酸乙二醇酯薄膜、聚邻苯二甲酸二烯丙酯薄膜、纤维素海绵薄膜、再生海绵薄膜、聚氨酯弹性体薄膜、苯乙烯丙烯共聚物薄膜、苯乙烯丁二烯共聚物薄膜、人造纤维薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯醇薄膜、聚异丁烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚乙烯醇缩丁醛薄膜、甲醛苯酚缩聚物薄膜、氯丁橡胶薄膜、丁二烯丙烯共聚物薄膜、天然橡胶薄膜、聚丙烯腈薄膜、丙烯腈氯乙烯共聚物薄膜中的任意一种。 When the first layer of polymeric material 42 or the second layer of polymeric material 44 without using a semiconductor composite material layer, its material is selected from polyimide film, aniline-formaldehyde resin film, a polyoxymethylene film, ethylcellulose film, polyamide film, a film of melamine formaldehyde, polyethylene glycol succinate ester film, cellulose film, cellulose acetate film, polyethylene adipate film, polyethylene film diallyl phthalate, cellulose sponge film, regenerated sponge film, a polyurethane elastomer film, styrene copolymer film, a styrene-butadiene copolymer film, rayon film, polymethyl methacrylate film, a polyvinyl alcohol film, polyisobutylene films , polyethylene terephthalate film, a polyvinyl butyral film, phenol formaldehyde polycondensate films, neoprene film, a propylene-butadiene copolymer film, a natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride copolymer film of any one. 此时,第一聚合物材料层42或第二聚合物材料层44厚度是100μm-500μm。 In this case, the thickness of the first polymer material 44 layer 42 or the second layer of polymeric material is 100μm-500μm.

[0087] 当本发明该实施方式的摩擦发电机的各层向下弯曲时,摩擦发电机中的第一聚合物材料层42、第二聚合物材料层44分别与居间电极层43表面相互摩擦产生静电荷,从而导致第一电极层41和居间电极层43之间,以及居间电极层43和第二电极层45之间出现电势差。 [0087] When the layers of the embodiment of the present invention a friction generator is bent downward, the friction in the generator 42 of the first layer of polymeric material, a second layer of polymeric material 44 and 43, respectively, the friction between the surface of the electrode layer intervening static charge, resulting in the first electrode layer between the electrode 41 and the intervening layer 43, and a potential difference occurs between the electrode 45 intervening layer 43 and the second electrode layer. 由于第一电极层41和居间电极层43之间,以及居间电极层43和第二电极层45之间电势差的存在,自由电子将通过外电路由电势低的一侧流向电势高的一侧,从而在外电路中形成电流。 Since the electrode layer 41 between the first electrode and the intervening layer 43, and a potential difference between the 45 intervening electrode layer 43 and the second electrode layer is present, free electrons will be routed through the foreign potential of the low potential side of the high flow side, thereby formed in the outer circuit current. 当本发明的摩擦发电机的各层恢复到原来状态时,这时形成在第一电极层41和居间电极层43之间,以及居间电极层43和第二电极层45之间的内电势消失,此时已平衡的第一电极层41和居间电极层43之间,以及居间电极层43和第二电极层45之间将再次产生反向的电势差,则自由电子通过外电路形成反向电流。 When the friction generator of the present invention, the layers restored to its original state, then formed between the first electrode layer 41 and the intermediate electrode layer 43, and the inner potential 43 and the second electrode layer 45 intervening between the electrode layer disappears , this time the balance between the first electrode layer 41 and the intermediate electrode layer 43, and the intervening electrode layer will again produce a reverse potential difference between the 43 and the second electrode layer 45, the free electrons form a reverse current through an external circuit . 通过反复摩擦和恢复,就可以在外电路中形成周期性的交流电信号。 By repeated friction and recovery, it can periodically formed in the outer circuit alternating current signal. 本发明该实施方式中,采用金属掺杂聚合物的半导体复合材料作为第一聚合物材料层42和/或第二聚合物材料层44,使其体积电阻率介于金属体积电阻率和绝缘材料体积电阻率之间的水平,因而可以有效降低发电机的工作内阻,在一定范围内可以提高摩擦发电机的负载能力。 The embodiment of the present invention, the use of metal-doped polymer composite material as the semiconductor layer of a first polymeric material 42 and / or the second layer of polymeric material 44, so that the volume resistivity and the volume resistivity of the insulating material between the metal level between the volume resistivity, which can effectively reduce the internal resistance of the generator is working, within a certain range can increase the friction of the generator load capacity.

[0088] 下面通过具体的实施例来阐述本发明的方法的实施,本领域技术人员应当理解的是,这不应被理解为对本发明权利要求范围的限制。 [0088] The following specific examples through to illustrate the implementation method of the present invention, those skilled in the art would understand that this should not be construed as limiting the scope of the invention as claimed.

[0089] 实施例中所用原料如下: [0089] examples of materials used are as follows:

[0090]表1 [0090] Table 1

Figure CN104426416AD00151

Figure CN104426416AD00161

[0093] 实施例I [0093] Example I

[0094] 摩擦发电机尺寸为3cmX3cm,总厚度大约是500μm。 [0094] Friction generator size 3cmX3cm, the total thickness is about 500μm. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 第一聚合物材料层12所用金属掺杂聚合物的半导体复合材料。 Semiconductor composite polymer layer 12 first polymeric material doped with a metal. 下面详细说明该摩擦发电机的制备方法。 The following detailed description of the preparation of friction generator.

[0095] 1.半导体复合材料的制备 Preparation [0095] A semiconductor composites

[0096] 采用7. 5g十二烷基硫酸钠对25g银颗粒(平均体积粒径50μm)进行表面处理,得到经过改性剂表面改性的金属颗粒。 [0096] 7. 5g using sodium dodecyl sulfate to 25g silver particles (volume average particle diameter 50μm) subjected to surface treatment to obtain surface-modified metal particles modifier. 将该经过改性剂表面改性的金属颗粒5g、固化剂(道康宁184)加入到95g聚二甲基硅氧烷(道康宁)中,得到混合浆料,其中聚二甲基硅氧烷与固化剂的质量比为10 :1。 The modifying agent after the surface-modified metal particles 5g, a curing agent (Dow Corning 184) was added to 95g of polydimethylsiloxane (Dow Corning) to give a mixed slurry, wherein the polydimethylsiloxane and curing agent mass ratio of 10: 1. 将所述浆料均匀地涂布在硅模板表面,经过真空脱气过程后,采用旋转涂覆的方式将多余的浆料去掉,形成一层薄的聚二甲基硅氧烷液体膜。 The slurry was uniformly coated on the surface of the silicon template, after vacuum degassing process, using the spin coating manner to remove excess slurry, the formation of a thin film of polydimethylsiloxane fluid. 将整个模板在85°C的环境中固化1小时之后,将聚二甲基娃氧烧膜从娃模板上剥离,制成一侧表面设置凸起高度为500nm的微纳凹凸结构的半导体复合材料薄膜(厚度为150um)。 After curing the entire template in 85 ° C environment for one hour will burn oxygen polydimethylsiloxane baby doll template stripped from the film, made a side surface of semiconductor composite bump height of 500nm uneven structure of micro-nano film (having a thickness of 150um).

[0097] 2.摩擦发电机的制备 Preparation [0097] 2. The friction generator

[0098] 采用上述半导体复合材料薄膜作为第一聚合物材料层12,其未设置微纳凹凸结构的表面上镀厚度IOOnm的铝薄膜,该铝薄膜即为第一电极层11。 [0098] With the above semiconductor composite film as a first layer of polymeric material 12, its aluminum plating film thickness on the surface of the micro-nano IOOnm uneven structure is not set, the aluminum film is the first electrode layer 11.

[0099] 采用厚度100μm的铜箔作为第二电极层13。 [0099] The copper foil of 100μm thickness as the second electrode layer 13. 按照第一聚合物材料层12的设有维纳凹凸结构的表面朝向第二电极层13,将第二电极层13叠放到第一聚合物材料层12上,得到摩擦发电机1#。 According to a first surface of the layer of polymeric material has a concavo-convex structure of Wiener 12 toward the second electrode layer 13, the second electrode layer 13 is superposed on the first layer of polymeric material 12 to give friction generator # 1. 该摩擦发电机的边缘用普通胶布密封。 Sealing edge of the friction generator with ordinary tape.

[0100] 该摩擦发电机在IV(电流-电压)的测量中表现出典型的开路特征。 [0100] The friction generator in the IV (current - voltage) measurements showed a typical open features. 1ΜΩ负载下使摩擦发电机发生周期的弯曲和释放,摩擦发电机的开路电压和工作内阻(摩擦发电机工作内阻可以通过直接测量工作状态下摩擦发电电阻的方式获得)分别为150V和75ΜΩ。 So 1ΜΩ friction generator under load bending and release cycle, the open circuit voltage and the internal resistance of the generator of friction (friction resistance generator can work in working condition by directly measuring frictional resistance of power available), respectively 150V and 75ΜΩ .

[0101] 实施例2 [0101] Example 2

[0102] 摩擦发电机尺寸为3cmX3cm,总厚度大约是500μm。 [0102] Friction generator size 3cmX3cm, the total thickness is about 500μm. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 第一聚合物材料层12所用金属掺杂聚合物的半导体复合材料。 Semiconductor composite polymer layer 12 first polymeric material doped with a metal. 下面详细说明该摩擦发电机的制备方法。 The following detailed description of the preparation of friction generator.

[0103] 1.半导体复合材料的制备 Preparation [0103] A semiconductor composites

[0104] 采用7. 5g十二烷基硫酸钠对25g铝颗粒(平均体积粒径50μm)进行表面处理, 得到经过改性剂表面改性的金属颗粒。 [0104] 7. 5g using sodium dodecyl sulfate to 25g aluminum particles (volume average particle diameter 50μm) subjected to surface treatment to obtain surface-modified metal particles modifier. 将该经过改性剂表面改性的金属颗粒5g加入到聚偏氟乙烯(95g)的二甲基乙酰胺溶液中,得到混合浆料。 The modifying agent after the surface-modified metal particles were added to 5g of polyvinylidene fluoride (95g) in dimethyl acetamide solution to obtain a mixed slurry. 将所述浆料均匀地涂布在硅模板表面,经过真空脱气过程后,采用旋转涂覆的方式将多余的浆料去掉,形成一层薄的聚偏氟乙烯液体膜。 The slurry was uniformly coated on the surface of the silicon template, after vacuum degassing process, using the spin coating manner to remove excess slurry, the formation of a thin liquid film of polyvinylidene fluoride. 将整个模板在85°C的环境中固化1小时之后,将聚偏氟乙烯膜从硅模板上剥离,制成一侧表面设置凸起高度为500nm的微纳凹凸结构的半导体复合材料薄膜(厚度为150um)。 After curing the entire template in 85 ° C environment for 1 hour, polyvinylidene fluoride film was peeled from the silicon template, made a side surface of semiconductor composite film projections height of 500nm of micro-nano uneven structure (thickness as 150um).

[0105] 2.摩擦发电机的制备 Preparation [0105] 2. The friction generator

[0106] 采用上述半导体复合材料薄膜作为第一聚合物材料层12,其未设置微纳凹凸结构的表面上镀厚度IOOnm的铝薄膜,该铝薄膜即为第一电极层11。 [0106] With the above semiconductor composite film as a first layer of polymeric material 12, its aluminum plating film thickness on the surface of the micro-nano IOOnm uneven structure is not set, the aluminum film is the first electrode layer 11.

[0107] 采用厚度100μm的铜箔作为第二电极层13。 [0107] The copper foil of 100μm thickness as the second electrode layer 13. 按照第一聚合物材料层12的设有维纳凹凸结构的表面朝向第二电极层13,将第二电极层13叠放到第一聚合物材料层12上,得到摩擦发电机1#。 According to a first surface of the layer of polymeric material has a concavo-convex structure of Wiener 12 toward the second electrode layer 13, the second electrode layer 13 is superposed on the first layer of polymeric material 12 to give friction generator # 1. 该摩擦发电机的边缘用普通胶布密封。 Sealing edge of the friction generator with ordinary tape.

[0108] 该摩擦发电机在IV(电流-电压)的测量中表现出典型的开路特征。 [0108] The friction generator in the IV (current - voltage) measurements showed a typical open features. 1ΜΩ负载下使摩擦发电机发生周期的弯曲和释放,摩擦发电机的开路电压和工作内阻(摩擦发电机工作内阻可以通过直接测量工作状态下摩擦发电电阻的方式获得)分别为90V和95ΜΩ。 So 1ΜΩ friction generator under load bending and release cycle, the open circuit voltage and the internal resistance of the generator of friction (friction resistance generator work by directly measuring the friction resistance generating mode operation state obtain) respectively 90V and 95ΜΩ .

[0109] 实施例3-4 [0109] Examples 3-4

[0110] 实施例3-4与实施例2的制备方法基本相同,不同之处如表2所示。 [0110] Example 3-4 Preparation Example 2 is basically the same, except as shown in Table 2.

[0111] 表2 [0111] Table 2

[0112] [0112]

Figure CN104426416AD00171

[0113] 1ΜΩ负载下使摩擦发电机3#和4#发生周期的弯曲和释放,3#摩擦发电机的开路电压和工作内阻分别为100V和70ΜΩ。 [0113] make 1ΜΩ load and friction generator 3 # 4 # generation cycle of bending and release, the open circuit voltage and work 3 # friction resistance generator respectively 100V and 70ΜΩ. 4#摩擦发电机的开路电压和工作内阻分别为90V 和90MΩ。 Open circuit voltage and operating resistance 4 # friction generator respectively 90V and 90MΩ.

[0114] 实施例5-8 [0114] Examples 5-8

[0115] 实施例5-8与实施例1的制备方法基本相同,不同之处如表3所不。 [0115] Examples 5-8 prepared in Example 1 is substantially the same, the difference is not as shown in Table 3.

[0116] 表3 [0116] Table 3

[0117] [0117]

Figure CN104426416AD00172

[0118] 1ΜΩ负载下使摩擦发电机5#_8#发生周期的弯曲和释放,5#摩擦发电机的开路电压和工作内阻分别为115V和85ΜΩ。 [01] so that the friction under load generator 1ΜΩ 5 # _8 # bending and release cycle, the open circuit voltage and operating resistance 5 # friction generator respectively 115V and 85ΜΩ. 6#摩擦发电机的开路电压和工作内阻分别为120V和80ΜΩ。 Open circuit voltage and operating resistance 6 # friction generator respectively 120V and 80ΜΩ. 7#摩擦发电机的开路电压和工作内阻分别为135V和80ΜΩ。 Open circuit voltage and resistance 7 # friction generator respectively 135V and 80ΜΩ. 8#摩擦发电机的开路电压和工作内阻分别为130V和85ΜΩ。 Open circuit voltage and internal resistance 8 # friction generator respectively 130V and 85ΜΩ.

[0119] 实施例9 [0119] Example 9

[0120] 摩擦发电机尺寸为3cmX3cm,总厚度大约是500μm。 [0120] Friction generator size 3cmX3cm, the total thickness is about 500μm. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 第一聚合物材料层12所用金属掺杂聚合物的半导体复合材料。 Semiconductor composite polymer layer 12 first polymeric material doped with a metal. 下面详细说明该摩擦发电机的制备方法。 The following detailed description of the preparation of friction generator.

[0121] 1.半导体复合材料的制备 Preparation [0121] A semiconductor composites

[0122] 采用50g十二烷基硫酸钠对50g银颗粒(平均体积粒径50μm)进行表面处理,得到经过改性剂表面改性的金属颗粒。 [0122] The sodium lauryl sulfate 50g 50g of silver particles (volume average particle diameter 50μm) subjected to surface treatment to obtain surface-modified metal particles modifier. 将该经过改性剂表面改性的金属颗粒lg、固化剂(道康宁184)加入到99g聚二甲基硅氧烷(道康宁)中,得到混合浆料,其中聚二甲基硅氧烷与固化剂的质量比为10:1。 The modifying agent after the surface-modified metal particles lg, a curing agent (Dow Corning 184) was added to 99g of polydimethylsiloxane (Dow Corning) to give a mixed slurry, wherein the polydimethylsiloxane and curing agent mass ratio of 10: 1. 将所述浆料均匀地涂布在硅模板表面,经过真空脱气过程后,采用旋转涂覆的方式将多余的浆料去掉,形成一层薄的聚二甲基硅氧烷液体膜。 The slurry was uniformly coated on the surface of the silicon template, after vacuum degassing process, using the spin coating manner to remove excess slurry, the formation of a thin film of polydimethylsiloxane fluid. 将整个模板在85°C的环境中固化1小时之后,将聚二甲基娃氧烧膜从娃模板上剥离,制成一侧表面设置凸起高度为500nm的微纳凹凸结构的半导体复合材料薄膜(厚度为150um)。 After curing the entire template in 85 ° C environment for one hour will burn oxygen polydimethylsiloxane baby doll template stripped from the film, made a side surface of semiconductor composite bump height of 500nm uneven structure of micro-nano film (having a thickness of 150um).

[0123] 2.摩擦发电机的制备 Preparation [0123] 2. The friction generator

[0124] 采用上述半导体复合材料薄膜作为第一聚合物材料层12,其未设置微纳凹凸结构的表面上镀厚度IOOnm的铝薄膜,该铝薄膜即为第一电极层11。 [0124] With the above semiconductor composite film as a first layer of polymeric material 12, its aluminum plating film thickness on the surface of the micro-nano IOOnm uneven structure is not set, the aluminum film is the first electrode layer 11.

[0125] 采用厚度100μm的铜箔作为第二电极层13。 [0125] The copper foil of 100μm thickness as the second electrode layer 13. 按照第一聚合物材料层12的设有维纳凹凸结构的表面朝向第二电极层13,将第二电极层13叠放到第一聚合物材料层12上,得到摩擦发电机9#。 According to a first surface of the layer of polymeric material has a concavo-convex structure of Wiener 12 toward the second electrode layer 13, the second electrode layer 13 is superposed on the first layer of polymeric material 12 to give friction generator 9 #. 该摩擦发电机的边缘用普通胶布密封。 Sealing edge of the friction generator with ordinary tape.

[0126] 该摩擦发电机在IV(电流-电压)的测量中表现出典型的开路特征。 [0126] The friction generator in the IV (current - voltage) measurements showed a typical open features. 1ΜΩ负载下使摩擦发电机发生周期的弯曲和释放,摩擦发电机的开路电压和工作内阻(摩擦发电机工作内阻可以通过直接测量工作状态下摩擦发电电阻的方式获得)分别为100V和90ΜΩ。 So 1ΜΩ friction generator under load bending and release cycle, the open circuit voltage and the internal resistance of the generator of friction (friction resistance generator can work in working condition by directly measuring frictional resistance of power available), respectively 100V and 90ΜΩ .

[0127] 实施例10 [0127] Example 10

[0128] 摩擦发电机尺寸为3cmX3cm,总厚度大约是500μm。 [0128] Friction generator size 3cmX3cm, the total thickness is about 500μm. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 第一聚合物材料层12所用金属掺杂聚合物的半导体复合材料。 Semiconductor composite polymer layer 12 first polymeric material doped with a metal. 下面详细说明该摩擦发电机的制备方法。 The following detailed description of the preparation of friction generator.

[0129] 1.半导体复合材料的制备 Preparation [0129] A semiconductor composites

[0130] 采用Ig十二烷基硫酸钠对50g银颗粒(平均体积粒径50μm)进行表面处理,得到经过改性剂表面改性的金属颗粒。 [0130] The Ig sodium dodecyl sulfate to 50g silver particles (volume average particle diameter 50μm) subjected to surface treatment to obtain surface-modified metal particles modifier. 将该经过改性剂表面改性的金属颗粒30g、固化剂(道康宁184)加入到50g聚二甲基硅氧烷(道康宁)中,得到混合浆料,其中聚二甲基硅氧烷与固化剂的质量比为10 :1。 The modifying agent after the surface-modified metal particles 30g, a curing agent (Dow Corning 184) was added to 50g of polydimethylsiloxane (Dow Corning) to give a mixed slurry, wherein the polydimethylsiloxane and curing agent mass ratio of 10: 1. 将所述浆料均匀地涂布在硅模板表面,经过真空脱气过程后,采用旋转涂覆的方式将多余的浆料去掉,形成一层薄的聚二甲基硅氧烷液体膜。 The slurry was uniformly coated on the surface of the silicon template, after vacuum degassing process, using the spin coating manner to remove excess slurry, the formation of a thin film of polydimethylsiloxane fluid. 将整个模板在85°C的环境中固化1小时之后,将聚二甲基硅氧烷膜从硅模板上剥离,制成一侧表面设置凸起高度为500nm的微纳凹凸结构的半导体复合材料薄膜(厚度为150um)。 After the entire template cured at 85 ° C for 1 hour in the environment, the polydimethylsiloxane template peeled from the silicon film, formed on one side surface of the semiconductor composite projection height of 500nm micro concavo-convex structure nano film (having a thickness of 150um).

[0131] 2.摩擦发电机的制备 Preparation [0131] 2. The friction generator

[0132] 采用上述半导体复合材料薄膜作为第一聚合物材料层12,其未设置微纳凹凸结构的表面上镀厚度IOOnm的铝薄膜,该铝薄膜即为第一电极层11。 [0132] With the above semiconductor composite film as a first layer of polymeric material 12, its aluminum plating film thickness on the surface of the micro-nano IOOnm uneven structure is not set, the aluminum film is the first electrode layer 11.

[0133] 采用厚度100μm的铜箔作为第二电极层13。 [0133] The copper foil of 100μm thickness as the second electrode layer 13. 按照第一聚合物材料层12的设有维纳凹凸结构的表面朝向第二电极层13,将第二电极层13叠放到第一聚合物材料层12上,得到摩擦发电机10#。 According to a first surface of the layer of polymeric material has a concavo-convex structure of Wiener 12 toward the second electrode layer 13, the second electrode layer 13 is superposed on the first layer of polymeric material 12, # 10 to give friction generator. 该摩擦发电机的边缘用普通胶布密封。 Sealing edge of the friction generator with ordinary tape.

[0134] 该摩擦发电机在IV(电流-电压)的测量中表现出典型的开路特征。 [0134] The friction generator in the IV (current - voltage) measurements showed a typical open features. 1ΜΩ负载下使摩擦发电机发生周期的弯曲和释放,摩擦发电机的开路电压和工作内阻(摩擦发电机工作内阻可以通过直接测量工作状态下摩擦发电电阻的方式获得)分别为75V和35ΜΩ。 So 1ΜΩ friction generator under load bending and release cycle, the open circuit voltage and the internal resistance of the generator of friction (friction resistance generator can work in working condition by directly measuring frictional resistance of power available) respectively 75V and 35ΜΩ .

[0135] 实施例11 [0135] Example 11

[0136] 摩擦发电机尺寸为3cmX3cm,总厚度大约是500μm。 [0136] Friction generator size 3cmX3cm, the total thickness is about 500μm. 该摩擦发电机1包括层叠设置的第一电极层11,第一聚合物材料层12,和第二电极层13。 The friction generator 1 includes a first stacked electrode layer 11 disposed, a first layer of polymeric material 12, and the second electrode layer 13. 第一聚合物材料层12所用金属掺杂聚合物的半导体复合材料。 Semiconductor composite polymer layer 12 first polymeric material doped with a metal. 下面详细说明该摩擦发电机的制备方法。 The following detailed description of the preparation of friction generator.

[0137] 1.半导体复合材料的制备 Preparation [0137] A semiconductor composites

[0138] 采用Ig十二烷基硫酸钠对30g银颗粒(平均体积粒径50μm)进行表面处理,得到经过改性剂表面改性的金属颗粒。 [0138] The Ig sodium dodecyl sulfate to 30g silver particles (volume average particle diameter 50μm) subjected to surface treatment to obtain surface-modified metal particles modifier. 将该经过改性剂表面改性的金属颗粒l〇g、固化剂(道康宁184)加入到90g聚二甲基硅氧烷(道康宁)中,得到混合浆料,其中聚二甲基硅氧烷与固化剂的质量比为10 :1。 The modifying agent after the surface-modified metal particles l〇g, a curing agent (Dow Corning 184) was added to 90g of polydimethylsiloxane (Dow Corning) to give a mixed slurry, wherein the polydimethylsiloxane and quality of curing agent ratio of 10: 1. 将所述浆料均匀地涂布在硅模板表面,经过真空脱气过程后,采用旋转涂覆的方式将多余的浆料去掉,形成一层薄的聚二甲基硅氧烷液体膜。 The slurry was uniformly coated on the surface of the silicon template, after vacuum degassing process, using the spin coating manner to remove excess slurry, the formation of a thin film of polydimethylsiloxane fluid. 将整个模板在85°C的环境中固化1小时之后,将聚二甲基硅氧烷膜从硅模板上剥离,制成一侧表面设置凸起高度为500nm的微纳凹凸结构的半导体复合材料薄膜(厚度为150um)。 After the entire template cured at 85 ° C for 1 hour in the environment, the polydimethylsiloxane template peeled from the silicon film, formed on one side surface of the semiconductor composite projection height of 500nm micro concavo-convex structure nano film (having a thickness of 150um).

[0139] 2.摩擦发电机的制备 Preparation [0139] 2. The friction generator

[0140] 采用上述半导体复合材料薄膜作为第一聚合物材料层12,其未设置微纳凹凸结构的表面上镀厚度IOOnm的铝薄膜,该铝薄膜即为第一电极层11。 [0140] With the above semiconductor composite film as a first layer of polymeric material 12, its aluminum plating film thickness on the surface of the micro-nano IOOnm uneven structure is not set, the aluminum film is the first electrode layer 11.

[0141] 采用厚度100μm的铜箔作为第二电极层13。 [0141] The copper foil of 100μm thickness as the second electrode layer 13. 按照第一聚合物材料层12的设有维纳凹凸结构的表面朝向第二电极层13,将第二电极层13叠放到第一聚合物材料层12上,得到摩擦发电机11#。 According to a first surface of the layer of polymeric material has a concavo-convex structure of Wiener 12 toward the second electrode layer 13, the second electrode layer 13 is superposed on the first layer of polymeric material 12, # 11 to give friction generator. 该摩擦发电机的边缘用普通胶布密封。 Sealing edge of the friction generator with ordinary tape.

[0142] 该摩擦发电机在IV(电流-电压)的测量中表现出典型的开路特征。 [0142] The friction generator in the IV (current - voltage) measurements showed a typical open features. 1ΜΩ负载下使摩擦发电机发生周期的弯曲和释放,摩擦发电机的开路电压和工作内阻(摩擦发电机工作内阻可以通过直接测量工作状态下摩擦发电电阻的方式获得)分别为Iiov和75ΜΩ。 So 1ΜΩ friction generator under load bending and release cycle, the open circuit voltage and the internal resistance of the generator of friction (friction resistance generator can work in working condition by directly measuring frictional resistance of power available) were Iiov and 75ΜΩ .

[0143] 在聚合物中掺杂导电金属颗粒,可以有效改善聚合物复合材料的电学性质,可以有效降低摩擦发电机的工作内阻。 [0143] doped conductive metal particles in the polymer, can effectively improve the electrical properties of polymer composite materials, can effectively reduce operating friction resistance generator. 当金属颗粒掺杂逐渐增加时,由于聚合物复合物材料静电性质明显受到影响,摩擦发电机的输出性能会呈现快速下降趋势。 When the metal particles are doped gradually increased, due to the electrostatic properties of polymer composite materials significantly affected the performance of the friction of the generator output will show a rapid decline. 同时,使用改性剂对金属颗粒的表面性质进行修饰,可以有效提高金属颗粒在聚合物中的分散效果,从而保证聚合物复合材料性质稳定性,均一性。 At the same time, the use of the surface properties of the modifier metal particles may be modified, can effectively improve the dispersion of metal particles in the polymer, polymer composite properties to ensure stability and uniformity.

[0144] 图9,图10,图11,图12所采用的摩擦发电机的基本结构与实施例1-11相同,尺寸为3cmX3cm,总厚度大约是500μm,不同之处在于聚合物材料层。 [0144] FIG 9, FIG 10, FIG. 11, the basic structure used in the generator of FIG. 12 friction same manner as in Example 1-11, size 3cmX3cm, a total thickness of about 500μm, except that the layer of polymeric material. 图9为采用Cu掺杂lwt% 聚合物(聚二甲基硅氧烷)半导体复合材料为聚合物材料层的摩擦发电机的开路电压输出值,图10为采用Cu掺杂lwt%聚合物半导体复合材料为聚合物材料层的摩擦发电机的IMΩ 负载电压输出值。 Figure 9 is the use of open-circuit voltage output value lwt% Cu-doped polymer (polydimethylsiloxane) semiconductor composite polymer material layer friction generator 10 for the introduction of Cu-doped polymer semiconductors lwt% IMΩ load voltage output composite material is a layer of polymeric material friction generator. 图11为常规聚合物材料层(聚二甲基硅氧烷,不掺杂金属)的摩擦发电机的开路电压输出值。 Open-circuit voltage output 11 is a conventional polymer material layer (polydimethylsiloxane, non-doped metal) friction generator. 图12为常规聚合物材料层(聚二甲基硅氧烷,不掺杂金属)的摩擦发电机的1ΜΩ负载电压输出值。 1ΜΩ load voltage output 12 is a conventional polymer material layer (polydimethylsiloxane, non-doped metal) friction generator.

[0145] 对比图9和图11,以及图10和图12可以看出,掺杂金属颗粒的半导体复合材料层改善了摩擦发电机的负载能力。 [0145] Comparative Figures 9 and 11, and 10 and 12 can be seen, the metal particles doped semiconductor layer of the composite material to improve the load capacity of friction generator. 由此可见,掺杂适量金属颗粒的半导体复合材料层将有效改善摩擦发电机的负载能力,即可以提高摩擦发电机对低阻抗电路的输出能力。 Thus, an appropriate amount of metal particles doped semiconductor composite layer will effectively improve the load capacity of the friction of the generator, which can increase friction generator of low impedance circuit output capacity.

Citas de patentes
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Clasificaciones
Clasificación internacionalB32B3/30, H02N1/04
Eventos legales
FechaCódigoEventoDescripción
18 Mar 2015C06Publication
15 Abr 2015C10Entry into substantive examination
28 Dic 2016C14Grant of patent or utility model