WO2014139364A1 - Générateur nanométrique chemisé à frottement de glissement - Google Patents

Générateur nanométrique chemisé à frottement de glissement Download PDF

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Publication number
WO2014139364A1
WO2014139364A1 PCT/CN2014/072833 CN2014072833W WO2014139364A1 WO 2014139364 A1 WO2014139364 A1 WO 2014139364A1 CN 2014072833 W CN2014072833 W CN 2014072833W WO 2014139364 A1 WO2014139364 A1 WO 2014139364A1
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Prior art keywords
friction
friction unit
generator according
unit
layer
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PCT/CN2014/072833
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English (en)
Chinese (zh)
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王中林
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国家纳米科学中心
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Publication of WO2014139364A1 publication Critical patent/WO2014139364A1/fr

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04—Friction generators

Definitions

  • the present invention relates to a generator, and more particularly to a jacketed sliding friction nanogenerator that converts mechanical energy of an external force into electrical energy.
  • BACKGROUND OF THE INVENTION Today, with the rapid development of microelectronics and materials technology, a large number of new types of microelectronic devices with multiple functions and high integration have been continuously developed, and have shown unprecedented application prospects in various fields of daily life. However, research on power systems that match these miniature electronic devices has lagged behind. Generally speaking, the power sources of these microelectronic devices are directly or indirectly derived from batteries. The battery is not only bulky, heavy, but also contains potentially toxic chemicals that are potentially harmful to the environment and the human body. Therefore, it has been extremely important to develop a technology that converts naturally occurring mechanical energy such as motion and vibration into electrical energy.
  • the current generators that can effectively convert the above mechanical energy into electrical energy are based on electromagnetic induction and are driven by turbines, steam turbines, diesel engines or other power machinery to convert energy generated by water flow, gas flow, fuel combustion or nuclear fission.
  • the mechanical energy is transmitted to the generator, which is then converted into electrical energy for use.
  • These generators all require relatively concentrated, high-intensity energy input, and they are basically unable to convert them into electrical energy for the kinetic energy generated by people's daily activities and with less intensity in nature.
  • conventional generators are bulky and complex in structure and cannot be used as power supply components for microelectronic devices at all.
  • the present invention provides a jacketed sliding friction nanogenerator capable of converting axial or rotational mechanical energy applied to a frictional nanogenerator into electrical energy.
  • a friction nanogenerator comprising: a first conductive element, a first friction layer placed in contact with an outer surface of the first conductive element, and a second conductive element in contact with an inner surface of the second conductive element a second friction layer, wherein the first friction layer includes a plurality of first friction units, the second friction layer includes a plurality of second friction units, and the outer surfaces of all the first friction units belong to the first curved surface, The inner surfaces of all the second friction units belong to the second curved surface, and the first curved surface and the outer curved surface thereof form an inner jacket layer structure; the outer surface of the first friction unit and the second friction unit The inner surface undergoes relative sliding friction under the action of an external force, and the friction area changes, and an electrical signal
  • At least a portion of the outer surface of the first friction unit is placed in contact with the inner surface of the second friction unit;
  • the outer surface of the first friction unit is completely separated from the inner surface of the second friction unit, and under the external force, at least part of the outer surface of the first friction unit and the second friction unit The inner surface contacts and relative sliding friction occurs;
  • the first curved surface and/or the second curved surface is a cylindrical surface, a tapered surface or a frustum surface; preferably, the first curved surface and/or the second curved surface has a circular cross section perpendicular to the axial direction. Shape, polygon or irregular shape;
  • the polygon is a regular polygon having equal sides
  • the first curved surface has the same shape as the second curved surface
  • the first curved surface and the second curved surface are coaxial sleeve layers;
  • the first curved surface and the second curved surface are coaxial cylindrical sleeve structures; preferably, the relative sliding friction between the first friction layer and the second friction layer is axial and/or radial ;
  • At least two of the first friction units are included in the first friction layer and/or at least two of the second friction units are included in the second friction layer;
  • an arrangement pattern of the first friction unit in the first friction layer corresponds to an arrangement pattern of the second friction unit in the second friction layer, so that the first friction When the rubbing layer is placed opposite to the second friction layer, the outer surface of each of the first friction units can be in contact with at least one inner surface portion of the second friction unit under the action of an external force;
  • the shape, size and/or arrangement pattern of the first friction unit and the second friction unit are the same, such that when the first friction layer is placed opposite to the second friction layer, under the action of an external force An outer surface of each of the first friction units can be substantially in full contact with an inner surface of one of the second friction units;
  • the arrangement pattern of the first friction unit and the second friction unit is an array-distributed arrangement
  • the arrangement pattern of the first friction unit and the second friction unit is a checkerboard arrangement such that a hole structure is formed in the first friction layer and the second friction layer;
  • the arrangement pattern of the first friction unit and the second friction unit is a strip shape of a space or a strip shape spirally arranged in the axial direction;
  • the first friction unit is a ring coaxial with the first curved surface
  • the second friction unit is a ring coaxial with the second curved surface
  • the longitudinal direction of the strip or the radial direction of the ring is perpendicular to the relative rubbing direction of the first friction unit and the second friction unit;
  • the width of the outer surface of the first friction unit and the inner surface of the second friction unit is 0.1 m-50 cm in a direction in which the two friction surfaces are opposite to each other ;
  • the width is lO m-lcm
  • the outer surface material of the first friction unit and/or the inner surface material of the second friction unit is an insulating material or a semiconductor material;
  • the insulating material is selected from the group consisting of aniline formaldehyde resin, polyoxymethylene, ethyl cellulose, polyamide nylon 11, polyamide nylon 66, wool and its fabric, silk and its fabric, paper, polyethylene glycol succinic acid Ester, cellulose, cellulose acetate, polyethylene glycol adipate, diallyl polyphthalate, regenerated cellulose sponge, cotton and its fabric, polyurethane elastomer, styrene-acrylonitrile copolymer , styrene-butadiene copolymer, wood, hard rubber, acetate, rayon, polymethyl methacrylate, polyvinyl alcohol, polyester, polyisobutylene, polyurethane elastic sponge, polyethylene terephthalate Ester, polyvinyl butyral, butadiene-acrylonitrile copolymer, neoprene, natural rubber, polyacrylonitrile, poly(vinylidene chloride-co-acrylon
  • the Group III and Group V compounds are selected from the group consisting of gallium arsenide and gallium phosphide;
  • the Group II and Group VI compounds are selected from the group consisting of cadmium sulfide and zinc sulfide;
  • the III-V compound and II- The solid solution composed of the group VI compound is selected from the group consisting of gallium aluminum arsenide and gallium arsenide phosphorus;
  • the first friction unit outer surface material and/or the second friction unit inner surface material is a non-conductive oxide, a semiconductor oxide or a complex oxide, including silicon oxide, aluminum oxide, manganese oxide, chromium oxide. Iron oxide, titanium oxide, copper oxide, zinc oxide, Bi02 and Y203; preferably, the outer surface of the first friction unit and/or the inner surface of the second friction unit are distributed with microstructures on the order of micrometers or submicrometers ;
  • the microstructure is selected from the group consisting of nanowires, nanotubes, nanoparticles, nanochannels, microchannels, nanocones, microcones, nanospheres, and microspheres;
  • the outer surface of the first friction unit and/or the inner surface of the second friction unit have an embellishment or coating of nano material
  • the outer surface of the first friction unit and/or the inner surface of the second friction unit are chemically modified such that the outer surface material of the first friction unit introduces a functional group and/or a negative charge that easily acquires electrons. And/or introducing a functional group and/or a positive charge that easily loses electrons on the inner surface material of the second friction unit;
  • the functional group which easily loses electrons includes an amino group, a hydroxyl group or a decyloxy group, and the functional group which easily obtains an electron includes an acyl group, a carboxyl group, a nitro group or a sulfonic acid group;
  • the first friction unit or the second friction unit is prepared by replacing the insulating material or the semiconductor material with a conductive material;
  • the conductive material of the first friction unit or the second friction unit is selected from the group consisting of a metal, a conductive oxide, and a conductive organic substance;
  • the first conductive element and the second conductive element are selected from the group consisting of a metal, a conductive oxide, and a conductive organic substance;
  • the metal is selected from the group consisting of gold, silver, platinum, aluminum, nickel, copper, titanium, chromium or selenium, and an alloy formed of the above metal, the conductive organic substance being selected from the group consisting of polypyrrole, polyphenylene sulfide, and poly Phthalocyanine compounds, polyanilines and polythiophenes;
  • the first conductive element is a rod, a film or a thin layer
  • the second conductive element is a thin film or a thin layer
  • the first conductive element, the second conductive element, the first friction layer and/or the second friction layer are rigid;
  • the first conductive element, the second conductive element, the first friction layer and/or the second friction layer are flexible;
  • the first conductive element is fixed on an inner surface of the first friction layer, and/or the second conductive element is fixed on an outer surface of the second friction layer;
  • the first friction layer further comprises a first filling medium for filling a space other than the first friction unit and/or the second friction layer further comprises a second filling medium for filling the second friction Space outside the unit;
  • the first filling medium and the second filling medium are composed of a material having a neutral friction electrode sequence with respect to the first friction unit and the second friction unit;
  • the material having a neutral friction electrode sequence is selected from the group consisting of polyisobutylene, polyurethane elastic sponge, polyethylene terephthalate, polyvinyl butyral, butadiene-acrylonitrile copolymer, and chloroprene.
  • the thickness of the first filling medium is less than or equal to the thickness of the first friction unit, and the thickness of the second filling medium is less than or equal to the thickness of the second friction unit;
  • the first filling medium and/or the second filling medium is a non-conductive solid, a non-conductive liquid, a non-conductive gas or a vacuum environment;
  • the first conductive element inner surface and/or the second conductive element outer surface further comprises a flexible or rigid support element;
  • the first conductive element is composed of a plurality of first conductive units having the same size and shape as the first friction unit, and/or the second conductive element has the same size as the second friction unit And the shape of the second conductive unit.
  • the jacketed sliding friction nanogenerator of the present invention When periodic axial or rotational power is applied to the jacketed sliding friction nanogenerator of the present invention, an AC pulse signal output can be formed between the first conductive element and the second conductive element. Compared with the prior art, the jacketed sliding friction nanogenerator of the present invention has the following advantages:
  • the two friction layers of the generator of the invention do not need a gap, and the devices with periodic full contact and full separation of the two friction layers are different in power generation principle, which provides a new design idea for the society.
  • the gapless design omits the installation of the elastic distance retaining member and also provides convenience for the packaging technology.
  • the former nano-generators are all flat-plate generators. In order to ensure their normal operation, it is necessary to provide an external force whose direction is periodically changed. However, the nano-generator of the present invention is driven not only by the axial translational power but also by the inner casing layer structure. It can work normally, and it can also make full use of the rotational power of the non-periodically changing direction, which greatly expands its application range.
  • the generator of the invention does not need large-scale, high-intensity energy input, and only the input mechanical energy can drive the relative sliding or rotating of the first friction layer and the second friction layer, thereby effectively collecting the natural environment and the daily life of people.
  • the mechanical energy of various strengths is converted into electrical energy to achieve efficient use of energy; moreover, the friction nano-generator includes a plurality of power generating units at the same time, which can greatly increase the output power, and the applied external force does not matter from that direction. It can have power output, which greatly improves the efficiency of the generator.
  • the generator of the invention does not need magnets, coils, rotors and the like, has a simple structure, a small volume, is easy to manufacture, is low in cost, and can be mounted on various devices which can cause relative sliding of the first friction layer and the second friction layer. It does not require a special working environment and is therefore highly compatible.
  • the generator of the present invention can be used not only as a small power source but also as a high power power generation.
  • the friction nanogenerator of the present invention can provide a DC current output through a bridge rectifier circuit for use in equipment requiring DC power.
  • FIG. 1 is a schematic cross-sectional view showing a typical structure of a friction nano-generator of the present invention
  • FIG. 2 is a schematic cross-sectional view showing the principle of power generation of a friction nano-generator of the present invention, wherein (a) is an original state diagram before the nano-generator starts working. (b) is the working state diagram of the nano-generator under external force, (c) is the working state diagram of the nano-generator under the action of the reverse external force; FIG.
  • FIG. 3 is the first surface and the first surface of the frictional nano-generator of the present invention
  • a schematic view of a typical shape of two curved surfaces wherein (a) is a cylindrical sleeve shape, (b) is a circular sleeve shape, (c) is an axial sectional view of an irregular cylindrical shape, and (d) is a first curved surface and a second curved surface shape.
  • FIG. 4 is a schematic diagram showing a typical cross section of a first curved surface and a second curved surface of a frictional nanogenerator in a direction perpendicular to an axis, wherein (a) is a coaxial rectangle, and (b) is Coaxial triangle, (c) is a coaxial octagon, (d) is a coaxial ellipse, (e) is a coaxial irregular pattern, (0 is a different axis circular;
  • FIG. 5 is a schematic view showing a layout scheme of an annular strip of a first friction unit and a second friction unit in a friction nanogenerator according to the present invention, wherein (a) is a layout of a first friction unit, and (b) is a layout of a second friction unit, ( c) a cross-sectional view of the frictional nano-generator along the axis perpendicular to the axis after assembly;
  • FIG. 8 is a friction nano power generation of the present invention. Schematic diagram of an array-distributed layout of a first friction unit and a second friction unit in the machine, shown in a schematic view after the first conductive element and the second conductive element are tiled;
  • FIG. 9 is a schematic view showing a typical structure of a flexible friction nano-generator of the present invention.
  • FIG. 10 is a schematic view showing a typical structure of an elastic support layer according to the present invention, wherein (a) is a state diagram in which the first friction unit and the second friction unit are separated, and (b) is slipped in the first friction unit and the second friction unit. State diagram of friction;
  • FIG. 11 is a schematic view showing a typical structure of a friction nano-generator including a filling medium according to the present invention, which is schematically shown after the first conductive element and the second conductive element are laid flat;
  • FIG. 12 is a diagram showing an open circuit voltage signal in accordance with an embodiment of the present invention.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The technical solutions in the embodiments of the present invention will be clearly and completely described in the following with reference to the accompanying drawings. It is apparent that the described embodiments are only a part of the embodiments of the invention, rather than all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
  • the present invention provides a simple structured friction nanogenerator that converts naturally occurring mechanical energy, such as motion and vibration, into electrical energy, which provides a matched power source for microelectronic devices.
  • the friction nanogenerator of the present invention utilizes a phenomenon in which surface charge transfer occurs when a material having a difference in polarity in a friction electrode sequence is contacted, and mechanical energy of an external force is converted into electric energy.
  • the “friction electrode sequence” as used in the present invention refers to the order in which the material is attracted according to the degree of attraction of the material. At the instant when the two materials are in contact with each other, the negative charge on the friction surface is from the polarity of the friction electrode sequence. The surface of the corrected material is transferred to the surface of the material having a relatively negative polarity in the friction electrode sequence. So far, there is no unified theory that can fully explain the charge transfer. Mechanisms, it is generally believed that this charge transfer is related to the surface work function of the material, and charge transfer is achieved by the transfer of electrons or ions on the friction surface.
  • the friction electrode sequence is only an empirically based statistical result, that is, the further the difference between the two materials in the sequence, the greater the positive and negative charge generated after the contact and the probability of the sequence being coincident, and Actual results are affected by a variety of factors, such as material surface roughness, ambient humidity, and relative friction.
  • the "contact charge” as used in the present invention refers to the charge on the surface of a material having a difference in polarity between two kinds of friction electrode sequences after contact friction and separation, and it is generally considered that the charge is only distributed on the surface of the material. The maximum depth of distribution is only about 10 nanometers. It should be noted that the sign of the contact charge is a sign of the net charge, that is, there may be a concentrated region of negative charge in a local region of the surface of the material with a positive contact charge, but the sign of the net charge of the entire surface is positive.
  • the thickness of the friction unit described in the present invention refers to the vertical distance from the lower end surface to the upper end surface of the friction unit; the thickness of the filling medium means the vertical distance from the lower end surface to the upper end surface of the filling medium is "polygon" according to the present invention. All graphics whose sides are straight and have more than two sides, where "normal polygons" are polygons of equal length.
  • the "irregular pattern" as used in the present invention means a pattern in which at least one side is curved and the number of side lengths is more than two.
  • the "cylinder surface" as used in the present invention refers to two types of curved surfaces, and the first type refers to a curved surface formed by moving a straight line or a curved line along a certain straight line along a certain curve, wherein the moving straight line may be a straight line or a curved line;
  • One type refers to a curved surface formed by a moving curve moving along a curve with a certain curve of the same shape.
  • a typical basic structure of the friction nanogenerator of the present invention includes: a first cylindrical conductive member 11, a plurality of first friction units 101 disposed on an outer surface of the first cylindrical conductive member 11, The friction unit constitutes a first friction layer 10; a second cylindrical conductive element 21, and a plurality of second friction units 201 disposed on an inner surface of the second cylindrical conductive element 21, the friction units forming a second friction layer 20; A friction unit 101 and a second friction unit 201 are oppositely disposed.
  • the outer surface of the first friction unit 101 and the inner surface of the second friction unit 201 are axially slidably rubbed, due to the first Friction slip
  • the element 101 and each of the second friction units 201 cause a change in the friction area of the two
  • the material of the first friction unit 101 and the material of the second friction unit 201 have a friction electrode order difference
  • the first conductive element 11 can pass through.
  • the second conductive element 21 outputs an electrical signal to the external circuit.
  • FIG. 2(a) is an original state diagram before the nanogenerator starts working, wherein the outer surface of the first friction unit 101 in the first friction layer 10 and the inner portion of the second friction unit 201 in the second friction layer 20 Place the surface contact.
  • the first conductive element 11 drives the first friction unit 101 to move in the axial direction of the cylinder, so that the outer surface of the first friction unit 101 and the second friction unit 201 Relative sliding friction occurs on the inner surface. Since the materials constituting the first friction unit 101 and the second friction unit 201 differ in the friction electrode sequence, the friction process causes surface charge transfer of both. In order to shield the electric field formed by the surface charges generated by the friction in the first friction unit 101 and the second friction unit 201 due to the misalignment, the free electrons in the second cylindrical conductive member 21 flow to the first through the external circuit. The conductive element 11 generates an instantaneous current.
  • the present invention does not limit that the first friction unit 101 and the second friction unit 201 maintain partial contact from beginning to end, as long as the two can contact and generate relative sliding friction tangential to the contact surface under external force, without external force.
  • the first friction unit 101 and the second friction unit 201 can be completely separated.
  • This design can meet the situation where interval power generation is required.
  • the friction process can have both contact friction and sliding friction.
  • the diameter of the first curved surface formed by the outer surface of the first friction unit 101 is smaller than the diameter of the second curved surface formed by the inner surface of the second friction unit 201, and the support can be supported.
  • the axes of the first friction unit 101 and the first conductive element 11 are provided as movable axes. In the initial position of the shaft, it can be ensured that a radial gap is formed between all the first friction units 101 and the second friction unit 201, and under the action of an external force, the movable shaft can adjust the position to make a part of the first friction unit.
  • the 101 is in contact with the second friction unit 201, and a sliding friction can be formed therebetween.
  • this embodiment is advantageous for generators used in combination with other products, and the first friction layer 10 and the second friction layer 20 may be respectively connected to two mutually separated components of other products, and the two components are utilized. Intermittent contact and relative sliding drive the generator to achieve intermittent power generation.
  • the first friction unit 101 and the second friction unit 201 are respectively composed of materials having different triboelectric characteristics, which means that the two are in different positions in the friction electrode sequence, so that the two are rubbing The process can generate contact charges on the surface.
  • Conventional insulating materials have triboelectric properties, which can be used as materials for preparing the first friction unit 101 and the second friction unit 201 of the present invention.
  • some common insulating materials are listed and sorted from positive polarity to negative polarity according to the friction electrode sequence.
  • aniline formaldehyde resin polyoxymethylene, ethyl cellulose, polyamide 11, polyamide 6-6, wool and its woven fabric, silk and its fabric, paper, polyethylene glycol succinate, cellulose, cellulose Acetate, polyethylene glycol adipate, diallyl polyphthalate, regenerated cellulose sponge, cotton and fabric, polyurethane elastomer, styrene-acrylonitrile copolymer, styrene-butadiene Copolymer, wood, hard rubber, acetate, rayon, polymethyl methacrylate, polyvinyl alcohol, polyester (polyester), polyisobutylene, polyurethane elastic sponge, polyethylene terephthalate, polyethylene Alcohol butadiene, butadiene-acrylonitrile copolymer, neoprene, natural rubber, polyacrylonitrile, poly(vinylidene chloride-co-acrylonitrile), polybisphenol A carbonate, polychloroether, poly Vinyliden
  • semiconductors and metals have triboelectric properties that tend to lose electrons relative to the insulator, often at the end of the list of friction electrode orders. Therefore, the semiconductor and the metal can also be used as a raw material for preparing the first friction unit 101 or the second friction unit 201.
  • Commonly used semiconductors include silicon, germanium; Group III and V compounds such as gallium arsenide, gallium phosphide, etc.; Group II and Group VI compounds such as cadmium sulfide, zinc sulfide, etc.; and III-V compounds and A solid solution composed of II-VI compounds, such as gallium aluminum arsenide, gallium arsenide phosphorus, and the like.
  • Non-conductive oxide, semiconductor oxide And complex oxides also have triboelectric properties and are capable of forming surface charges during the rubbing process, and thus can also be used as the friction layer of the present invention, such as oxides of manganese, chromium, iron, copper, and also include silicon oxide, manganese oxide, Chromium oxide, iron oxide, copper oxide, zinc oxide, Bi02 and Y203; commonly used metals include gold, silver, platinum, aluminum, nickel, copper, titanium, chromium or selenium, and alloys formed from the above metals.
  • the friction layer material which easily loses electrons
  • ITO indium tin oxide
  • conductive organic materials are conductive polymers, including self-polypyrrole, polyphenylene sulfide, Polyphthalocyanine compounds, polyanilines and/or polythiophenes.
  • the conductive element and the friction layer can be combined into one, which simplifies the preparation process, reduces the cost, and is more advantageous for industrial promotion and application.
  • the first friction unit 101 and the second friction unit 201 can be prepared by selecting a suitable material according to actual needs to obtain a better output effect.
  • the material having the negative polarity friction electrode sequence is preferably polystyrene, polyethylene, polypropylene, polydiphenylpropionate carbonate, polyethylene terephthalate, polyimide, polyvinyl chloride, polydimethylene Siloxane, polychlorotrifluoroethylene and polytetrafluoroethylene and parylene, including parylene C, parylene N, parylene D, parylene HT or parylene AF4;
  • the friction electrode sequence material is preferably aniline formaldehyde resin, polyoxymethylene, ethyl cellulose, polyamide nylon 11, polyamide nylon 66, wool and its fabric, silk and its fabric, paper, polyethylene glycol succinate, cellulose , cellulose acetate, polyethylene glycol adipate, diallyl polyphthalate, regenerated cellulose sponge, cotton and its fabric, polyurethane elastomer, styrene-acrylonitrile copolymer, styrene - But
  • the outer surface of the first friction unit 101 and/or the inner surface of the second friction unit 201 may be physically modified to have a micro-array or micro-micron array of microstructures on the surface thereof to increase the first friction unit 101 and the first The contact area between the two rubbing units 201, thereby increasing the amount of contact charge.
  • Specific modification methods include photolithography, chemical etching, and ion etching. This can also be achieved by means of embellishment or coating of nanomaterials. It is also possible to chemically modify the surfaces of the first friction unit 101 and/or the second friction unit 201 that are in contact with each other, so as to further increase the amount of charge transfer at the moment of contact, thereby increasing the contact charge density and the output power of the generator.
  • Chemical modification is further divided into the following two types:
  • One method is to introduce a more electron-releasing functional group on the surface of the positive polarity material for the materials of the first friction unit 101 and the second friction unit 201 that are in contact with each other (ie, strong Electron group), or the introduction of more electron-friendly functional groups (strong electron-withdrawing groups) on the surface of a material with a negative polarity, can further increase the amount of charge transferred when sliding each other, thereby increasing the friction charge density and the output of the generator. power.
  • Strong electron donating groups include: amino group, hydroxyl group, decyloxy group, etc.
  • strong electron withdrawing group includes: acyl group, carboxyl group, nitro group, sulfonic acid group and the like.
  • the introduction of the functional group can be carried out by a conventional method such as plasma surface modification. For example, a mixture of oxygen and nitrogen can be used to generate a plasma at a certain power to introduce an amino group on the surface of the friction layer material.
  • Another method is to introduce a positive charge on the surface of the friction layer material having a positive polarity and a negative charge on the surface of the friction layer material having a negative polarity.
  • it can be achieved by chemical bonding.
  • ethyl orthosilicate in English abbreviated as TEOS
  • hydrolysis-condensation in English abbreviated as sol-gel
  • Gold nanoparticles containing hexadecanoyltrimethylammonium bromide (CTAB) on the outer surface may also be modified by gold-sulfur bonding on the metal gold thin film layer, since hexadecanyltrimethylammonium bromide is a cation Therefore, the entire friction layer becomes positively charged.
  • CTAB hexadecanoyltrimethylammonium bromide
  • the thicknesses of the first friction unit 101 and the second friction unit 201 have no significant effect on the implementation of the present invention, except that factors such as friction unit strength and power generation efficiency need to be comprehensively considered in the setting process.
  • the friction layer of the present invention is a film or a thin layer having a thickness of from 10 nm to 2 cm, preferably from 50 nm to 5 mm, and these thicknesses are applicable to all of the technical solutions in the present invention.
  • the outer surfaces of all the first friction units 101 belong to the first curved surface
  • the inner surfaces of all the second friction units 201 belong to the second curved surface
  • the first curved surface and the second curved surface on the outer side thereof form the proposed surface of the present invention.
  • the sleeve structure is such that the first friction unit 101 and the second friction unit 201 can directly contact or contact under the action of an external force, and achieve relative sliding friction by rotation and/or axial translation.
  • the occurrence of sliding friction is only two sides The contact is related, regardless of the shape of the friction surface itself. Therefore, the first curved surface and the second curved surface in the present invention may have various shapes such as a cylindrical surface, a tapered surface, or a frustum surface.
  • Figure 3 shows several typical shapes, where Figure 3 (a) is a cylindrical surface, Figure 3 (b) is a truncated cone, and it can also be an irregular cylinder, as shown in Figure 3 (c) A lantern-like cylinder formed by a curve around a straight line.
  • the shapes of the two surfaces can be the same or different (see Figure 3 (d), where the first surface is a cylindrical surface and the second surface is an elliptical cylinder), as long as the two surfaces can contact under the force and Just slide it.
  • Its cross-section perpendicular to the axial direction can also take various shapes, such as circular, elliptical, polygonal or irregular patterns (see Figure 4 (a) - (0), where the polygon can be a regular rectangle, triangle, six For the shape of the triangle, the octagon, etc., the irregular shape can be other shapes such as a fan shape. These shapes can be selected according to the space of the actual application environment.
  • the first surface and the second surface have the same shape to ensure the first The friction area of one friction unit 101 and the second friction unit 201 is the largest.
  • the first curved surface and the second curved surface may be coaxial or different axes.
  • the two are coaxial, such as a coaxial cylindrical sleeve structure, it is easier to realize the axis between the first friction layer 10 and the second friction layer 20. Relative sliding friction to and/or radial.
  • the two axes are different (see Fig. 3 (d) and Fig. 4 (0), the sliding between the first friction unit 101 and the second friction unit 201 can still be accomplished by the relative movement of the two shafts. Therefore, whether the first curved surface and the second curved surface are coaxially arranged depends on the specific requirements of the applied environment.
  • the connection method for realizing the relative sliding friction of the two curved surfaces is the most conventional way in the field, for example. It is capable of completing various bearing connections such as plane rotation, axial sliding and/or spiral sliding.
  • the first friction unit 101 and the second friction unit 201 are placed in contact, and whether or not an external force is applied thereto, at least a portion of the first friction unit 101 and the second friction unit 201 are kept in surface contact.
  • This is the most typical structure of the generator of the present invention.
  • the present invention does not limit that the first friction unit 101 and the second friction unit 201 maintain surface contact from beginning to end, as long as at least part of the first friction unit 101 can be in contact with the second friction unit 201 under the action of an external force, and relative sliding friction occurs. Yes, but no external force In use, the first friction unit 101 and the second friction unit 201 can be completely separated. This design can meet the situation where interval power generation is required. Moreover, the friction process can have both contact friction and sliding friction.
  • This embodiment is advantageous for generators used in combination with other products.
  • the first friction unit 101 and the second friction unit 201 can be respectively connected to two mutually separated components of other products, and the intermittent use of the two components is utilized. Contact and relative sliding to drive the generator to work, thus achieving intermittent power generation.
  • FIG. 5 shows a typical arrangement of the first friction unit 101 and the second friction unit 201.
  • the first friction unit 101 is arranged in an annular strip at intervals on the outer surface of the first conductive member 11, and the annular plane formed is perpendicular to the axial direction (see FIG. 5(a)), thereby constituting a discontinuous first friction.
  • the second friction unit 201 is also arranged at the same inner surface of the second conductive member 21 at the same thin strips (see FIG. 5(b), which is a schematic structural view, and the number and size of the friction units cannot be judged therefrom.
  • the second friction layer 20 is also discontinuous; thus, when the first friction layer 10 and the second friction layer 20 are placed opposite each other (see perpendicular to the axial direction)
  • the cross-sectional view of Fig. 5 (c)) ensures that each of the first friction units 101 is at least partially in contact with a second friction unit 201.
  • each of the first friction unit 101 and the corresponding second friction unit 201 can be precisely controlled, the friction units can be brought into full contact, and the area of misalignment/mismatch caused by the sliding friction is maximized. , such that the charge density generated during the rubbing process The total power is the largest.
  • the shape, size and position of each friction unit cannot be completely and precisely controlled, it is ensured that most of the first friction unit 101 can be at least partially in contact with a second friction unit 201, which enables the two to Charge transfer occurs during the sliding friction to achieve the object of the present invention.
  • Fig. 6 shows the case where the first friction unit 101 and the second friction unit 201 are arranged in an axially elongated shape.
  • the advantage of a generator with this design is that it can be driven not only by the axial force, but also by the rotational power that is tangent to the cylindrical surface, even when the two forces act simultaneously, the generator can still operate normally. This has greatly expanded the range of applications for nanogenerators.
  • the strip-shaped friction units may be arranged to be spirally arranged in the axial direction.
  • the first friction unit 101 and the second friction unit 201 adopt a checkerboard layout design, and also have the advantage of being able to be driven by both axial and tangential forces.
  • the tiled pattern of the first conductive element 11 and the second conductive element 21 of the barrel structure is shown, see FIG. It can be seen that the first friction unit 101 and the second friction unit 201 are arranged in a regular checkerboard shape, so that a regular hole structure is formed in the first friction layer 10 and the second friction layer 20, and the hole structure ensures the first When the frictional layer 10 and the second friction layer 20 are relatively slidably rubbed, the frictional area can be changed, so that an electrical signal can be generated to be output to the outside.
  • This checkerboard arrangement gives the present invention another very significant advantage in that the first friction unit 101 can be caused as long as a small relative slip between the first friction layer 10 and the second friction layer 20 occurs.
  • the change in the contact area with the second friction unit 201, that is, the generator of the present invention can still operate normally under the action of a relatively small driving force; or between the first friction layer 10 and the second friction layer 20
  • This embodiment is particularly important where the relative displacement is limited.
  • the array-distributed layout Similar to the checkerboard layout is the array-distributed layout, see Figure 8 for details.
  • This layout differs from the checkerboard layout in that there is no contact between the adjacent first friction units 101, and likewise, there is no contact between the adjacent second friction units 201.
  • the cross-sectional shape of the array unit ie, the first or second friction unit
  • the cross-sectional shape of the array unit may be a rectangle, a square, a circle, a triangle Shapes, etc., can also be irregular patterns; array elements can also be arranged in a pattern such as rectangles, squares, circles, triangles, and the like.
  • the layout is more convenient to prepare, which is beneficial to industrial promotion and application.
  • first friction unit 101 and the second friction unit 201 are the same or similar in the above embodiment, those skilled in the art should recognize that these are not the generators of the present invention that can work normally.
  • the necessary condition is that the generator of the present invention can output an electric signal as long as the frictional area of the portion of the first friction unit 101 and the second friction unit 201 during the sliding friction can be changed. Therefore, those skilled in the art can completely design the shape, size and arrangement of the first friction unit 101 and the second friction unit 201 according to actual needs, and these designs are all guided by the principles disclosed by the present invention. It should fall within the scope of protection of the present invention.
  • the inventors have found that the greater the density of the friction elements contained in the friction layer, the greater the amount of charge generated after sliding friction, and the relationship between them is linearly positively correlated, while the open circuit voltage is decreased. Therefore, in order to obtain a larger output charge density, it is preferable that at least two first friction units 101 are included in the first friction layer 10, and at least two second friction units 201 are included in the second friction layer 20, more preferably in operation.
  • the outer surface of each of the first friction units 101 can be in substantially complete contact with the inner surface of a second friction unit 201.
  • the width of the first friction unit 101 and the second friction unit 201 in the direction of friction with respect to the two is generally not limited, and may be determined according to the size of the generator, preferably 0.1 m-5 cm, more preferably 10 m-lcm, The inventors have found that when the size is equivalent to the thickness of the friction unit, the influence of the density of the friction unit in the friction layer on the amount of surface charge is more remarkable.
  • the appropriate friction unit size and arrangement density can be selected according to the law during the application process.
  • the invention does not limit that the first friction unit 101 and the second friction unit 201 must be hard materials, and a flexible material may also be selected, because the hardness of the material does not affect the sliding friction effect between the two, for example, our common animal fiber. It is very soft, but generates a considerable amount of static charge during friction with each other, so that a person skilled in the art can select a hard or flexible material according to the actual situation.
  • Figure 9 shows a cylindrical friction nano-generator made of ultra-soft and elastic polymer material. The advantage of this generator is that the soft and thin friction layer is deformed by a slight external force. This deformation causes the phases of the two friction layers For displacement, the electrical signal is output outward by sliding friction.
  • the use of flexible materials makes the nanogenerators of the present invention also very widely used in the biological and medical fields. In the process of use, it can also be made of a polymer material which is ultra-thin, soft, elastic and/or transparent.
  • both the first conductive layer and the second conductive layer can be composed of a soft conductive polymer material to improve the flexibility and deformability of the generator as a whole.
  • all the structures disclosed in the present invention can be made of corresponding super soft and elastic materials to form a flexible and/or stretchable nano-generator, which will not be described here, but derived therefrom.
  • Various designs should be included within the scope of this patent.
  • the first conductive element 11 and the second conductive element 21 are two electrodes of the generator, and may be selected from a metal, a conductive organic substance or a conductive oxide as long as they have characteristics capable of conducting electricity, and commonly used metals include gold, silver, platinum, and the like.
  • the conductive member is in close contact with the surface of the corresponding friction unit to ensure charge transfer efficiency; the specific deposition method of the conductive material may be electron beam evaporation, plasma sputtering, magnetron sputtering or evaporation, or directly using metal.
  • the board acts as a conductive element.
  • the conductive element need not necessarily be rigid or flexible, as the flexible conductive element can also serve to support and conduct the friction layer.
  • the electrically conductive element may be a film or a thin layer, and the thickness may be selected from the range of 10 nm to 5 cm, preferably 50 nm to 1 cm, preferably 100 nm to 5 mm, preferably 1 m to 1 mm.
  • the first conductive member on the inner side may also be a solid rod (see Fig. 4(c)).
  • the conductive elements may have the same distribution pattern as their corresponding friction layers, and the specific preparation may be by conventional mask-etching, sputtering deposition, and the like in semiconductor fabrication.
  • the electrically conductive element may also consist of a number of electrically conductive elements (111 and 211) of the same size and shape as the respective frictional unit, i.e. the electrically conductive element is not continuous.
  • This embodiment is more suitable for the case where the support members (103 and 203) are further provided on the other side of the discontinuous conductive member (see Fig. 10), the inner jacket layer structure is formed by the support material, and the support material is formed.
  • the desired conductive element and the friction layer can be formed by a conventional method in the art, such as etching, sputtering deposition, or the like.
  • An advantage of this embodiment is that the elasticity of the support member radius can be expanded and contracted, and the first friction unit 101 and the second friction unit 201 can be realized with the first curved surface and the second curved surface being coaxial. Contact and separation. Specifically, the first friction unit 101 is supported on the elastic supporting layer 103 through the first conductive unit 111 deposited thereon, and the second friction unit 201 is supported on the inner surface of the supporting member 203 through the second conductive unit 211, thereby forming Coaxial inner jacket layer structure. In the initial state, the first friction unit 101 is separated from the second friction unit 201 by the action of the elastic supporting layer 103 (see FIG.
  • the force applying member is disposed inside the elastic supporting layer 103,
  • the urging member can expand the elastic supporting layer to enlarge the radius of the first curved surface, and simultaneously drive the first friction unit 101 to contact with the second friction unit 201 and generate sliding friction (see FIG. 10(b)), thereby generating electricity.
  • the signal is sent to the external circuit.
  • the force applying member may be a member that is conventional in the art and capable of controlling the radius, such as a member similar to a keel of an umbrella, or a combination of a plurality of thrust applying members of a length that can be stretched.
  • the first conductive element 11 and the second conductive element 21 may be connected to the external circuit in such a manner as to be connected to the external circuit through a wire or a metal film.
  • FIG. 11 is a schematic view showing another typical structure of the friction nanogenerator of the present invention.
  • the first conductive element and the second conductive material forming the sleeve structure are still shown.
  • the main structure is the same as that of the embodiment shown in FIG. 7 , except that: the space of the first friction layer 10 except the first friction unit 101 is filled with the first filling medium 102 , and the second friction layer 20 is divided by the first The space outside the two friction units 201 is filled with a second filling medium 202.
  • the first filling medium 102 and the second filling medium 202 are materials having a neutral friction electrode sequence with respect to the friction unit material, and are not easily generated during the friction process. Charge transfer.
  • the addition of the first filling medium 102 and the second filling medium 202 greatly enhances the mechanical strength of the first friction layer 10 and the second friction layer 20, thereby enabling the generator of the present invention to be used in a wider range of fields and having more Long life.
  • the present embodiment is a checkerboard layout, it is apparent that it is also possible to add a filling medium in other embodiments of the present invention, and the first filling medium 102 and the second filling
  • the charging medium 202 may be added at the same time or may be separately added as appropriate, which does not affect the normal operation of the generator of the present invention.
  • the materials of the first filling medium 102 and the second filling medium 202 do not have to be the same, and both can be selected from the following ranges: polyisobutylene, polyurethane elastic sponge, polyethylene terephthalate, polyvinyl alcohol Butyraldehyde, butadiene-acrylonitrile copolymer, neoprene, natural rubber, polyacrylonitrile, poly(vinylidene chloride-co-acrylonitrile), polybisphenol A carbonate, polychloroether, polyvinylidene chloride Ethylene and poly(2,6-dimethylpolyphenylene oxide).
  • the first filling medium 102 and the second filling medium 202 may also be liquid or gas, and may be vacuum if necessary. It should be noted that the material of the filling medium should not be prone to charge transfer during the rubbing process.
  • the shapes of the first filling medium 102 and the second filling medium 202 are basically the same as the requirements for the strength of the friction layer, and can be adjusted according to actual conditions.
  • the height of the filling medium is lower than the corresponding friction unit, and the arrangement can be effective while ensuring the working efficiency of the generator. Improve the strength of the friction layer.
  • the filling medium is generally shorter than the height of the friction unit, but can also be substantially the same, which is suitable for the case where the strength of the friction unit material itself is small.
  • the filling medium is composed of a material having a relatively neutral triboelectric property, even if friction occurs with the friction unit in the other friction layer during sliding, the friction is not easily generated due to its characteristic of charge transfer. It does not have a significant impact on the overall efficiency of the generator.
  • the inner surface of the first conductive element and/or the outer surface of the second conductive element may also include flexibility or A rigid support member, such as support member 103 in Figure 4 (b) and support layers 103 and 203 in Figure 10.
  • the main function of the supporting member is to increase the mechanical strength of the generator, and the nature of the material itself is not particularly limited, and a semiconductor or an insulator is preferably used.
  • the support element outside the second conductive element can also be layered for use as an encapsulation layer to protect the core components of the generator and extend its life.
  • the first conductive element is made of a metal copper foil having a size of 6.4 cm X 3.8 cm
  • the second conductive element is a metal aluminum sheet of 6.4 cm X 4.5 cm
  • the material of the first friction unit is Teflon.
  • polytetrafluoroethylene film the material of the second friction unit is polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • Teflon was made into two strip-shaped film structures with length, width and height of 6cm, 1.6cm and 0.2cm, respectively, and was pasted on the copper sheet with conductive paste in the manner of Fig. 6, and polyethylene terephthalate was used. The same size and spacing are distributed over the aluminum sheet.
  • the copper sheet is pasted with the Teflon side facing outward, and a plastic rod having a diameter of about 0.6 cm and a length of 10 cm is rolled into a cylindrical shape and fixed at both ends by a strip.
  • the aluminum sheet is pasted with polyterephthalic acid.
  • the ethylene glycol is rolled inwardly around the copper cylinder formed before, and is rolled into a cylindrical shape with a slightly larger diameter, and the position is adjusted so that two polyethylene terephthalate strips are respectively opposed to the two Teflon strips. It can be surface-contacted, and after adjusting the position, the cylinder is fixed by a rubber strip, and the outer side is fixed on the insulating support by glue.
  • the polyethylene terephthalate strips and the polytetrafluoroethylene strips are placed opposite each other so that the two are as completely facing as possible.
  • An external force is applied to the plastic rod by the motor to rotate at an average linear velocity of 0.6 m/sec. Sliding friction occurs between the polyethylene terephthalate strip and the polytetrafluoroethylene strip, and the friction area changes periodically.
  • the frictional nanogenerator is driven to work, and the resulting open circuit voltage output is shown in FIG.
  • This embodiment is basically the same as the first embodiment except that the silicon wafer with a thickness of 600 ⁇ is used as the second friction unit material, and a layer of photoresist is spin-coated on the surface of the silicon wafer, and photolithography is used for photolithography.
  • a square window array having a side length on the order of micrometers or sub-micrometers is formed on the glue, and the lithographically completed silicon wafer is subjected to chemical etching of hot potassium hydroxide to form an array of pyramid-shaped recessed structures at the window.
  • the pattern is the same thin layer of checkerboard Ag, which simultaneously acts as the first conductive element.
  • This embodiment is basically the same as Embodiment 1, except that a ring-shaped gold Au strip as shown in FIG. 5 is formed outside the hexagonal column of the polychloroether casing by a conventional method such as mask-etching-metal deposition-mask removal.
  • the width of the strip in the axial direction is approximately 100 ⁇ .
  • a polydimethylsiloxane (PDMS) annular strip is prepared as a first friction unit on the top of the gold strip by spin coating and etching, and the surface is further processed by inductively coupled plasma etching to prepare the nanowire.
  • PDMS polydimethylsiloxane
  • the specific steps are as follows: depositing about 10 nm thick gold on the surface of the PDMS by a sputter, then placing the PDMS film in an inductively coupled plasma etching machine, etching the gold deposited side, and introducing 0 2 , Ar and CF 4 gas, the flow rate is controlled at 10sccm, 15sccm and 30sccm, the pressure is controlled at 15mTorr, the working temperature is controlled at 55 °C, 400 watts of power is used to generate plasma, and 100 watts of power is used to accelerate the plasma. An etch of about 5 minutes was performed to obtain a PDMS nanorod array having a length substantially perpendicular to the film layer of about 1.5 microns.
  • a PET annular strip similar in size and shape to the PDMS strip is formed by spin coating and etching on the aluminum sheet, and the modified aluminum sheet is folded into a polychloroether sleeve.
  • the matching hexagonal cylinder faces bring the PDMS strip into contact with the PET strip surface (structure is similar to Figure 4-c).
  • a periodic axial external force of 10 m/s is applied to the polychloroether casing, so that the PDMS strip and the PET strip are subjected to sliding friction, and the contact area between the two changes periodically, thereby outputting a periodic output. electric signal. Due to the microstructure of the PDMS film surface, the contact area with the PET is increased, and the output performance of the generator is improved.
  • a copper metal film having a thickness of ⁇ is used as a second conductive element, and a predetermined pattern of holes having a diameter of about 2 m is formed on the surface thereof by a photolithographic mask, and a surface of the metal copper is exposed through the bottom of the hole, and then by vapor deposition.
  • a zinc oxide rod having a length of about ⁇ is selectively deposited at the pattern.
  • a layer of polyacrylonitrile is uniformly deposited on the device obtained above, and then the filling material is subjected to treatment such as heating or exposure, and after the mechanical strength reaches the required range,
  • the plasma dry etching technique is used to uniformly remove the top of the filling material to a suitable thickness, so that the top of the zinc oxide is exposed to an appropriate height.
  • a second friction layer is required.
  • a metal aluminum column with a diameter of 2 m is used as the first conductive element, and a similar pattern on the surface of the metal copper sheet is formed on the surface by a photolithographic mask, and a length of about ⁇ is deposited on the pattern by sputtering.
  • the metal aluminum column is then filled with polyacrylonitrile by a ruthenium film, etching process or the like in a manner similar to that of the second friction layer to form a continuous first friction layer.
  • the lead wire is connected to the external circuit on the metal copper layer and the metal aluminum layer, and the metal copper film is formed around the aluminum column to form a jacket structure, so that the zinc oxide column and the aluminum column face each other face to face, that is, the invention is completed.
  • Generator preparation The axial translational power and the tangential rotational power are simultaneously applied to the aluminum column, wherein the axial translational power is a periodic reciprocating power. Under the action of an external force, the first friction layer and the second friction layer slide relative to each other and output an electrical signal to the external circuit.
  • a filling layer is used to encapsulate the friction layer of the generator, which can significantly increase the mechanical strength of the friction unit and prolong the working life of the generator.
  • the friction nano-generator of the invention can use the translational motion to generate electric energy by the generator, provide power for the small-sized electric appliance, and does not need a power supply such as a battery, and is a convenient generator.
  • the friction nano-generator of the invention is simple in preparation method and low in preparation cost, and is a widely used friction nano-generator and generator.

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Abstract

La présente invention concerne un générateur nanométrique chemisé à frottement de glissement, comportant un premier élément conducteur (11), une première couche (10) de frottement qui est placée en contact avec la surface extérieure du premier élément conducteur, un deuxième élément conducteur (21) et une deuxième couche (20) de frottement qui est placée en contact avec la surface intérieure du deuxième élément conducteur, la première couche de frottement comportant une pluralité de premières unités (101) de frottement et la deuxième couche de frottement comportant une pluralité de deuxièmes unités (201) de frottement; de plus, les surfaces extérieures de toutes les premières unités de frottement appartiennent à une première surface courbe; les surfaces intérieures de toutes les deuxièmes unités de frottement appartiennent à une deuxième surface courbe; la première surface courbe et la deuxième surface courbe à l'extérieur de la première surface courbe forment une structure chemisée intérieurement et extérieurement; les surfaces extérieures des premières unités de frottement et les surfaces intérieures des deuxièmes unités de frottement génèrent un frottement de glissement relatif; en même temps, la zone de frottement subit une variation; et un signal électrique est délivré vers un circuit extérieur par l'intermédiaire du premier élément conducteur et du deuxième élément conducteur. Le générateur nanométrique à frottement peut être utilisé comme une nouvelle technologie énergétique ou une technologie de détection.
PCT/CN2014/072833 2013-03-13 2014-03-04 Générateur nanométrique chemisé à frottement de glissement WO2014139364A1 (fr)

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