CN102683578A - Manufacturing method of zinc oxide piezoelectric wire - Google Patents
Manufacturing method of zinc oxide piezoelectric wire Download PDFInfo
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- CN102683578A CN102683578A CN2011101620474A CN201110162047A CN102683578A CN 102683578 A CN102683578 A CN 102683578A CN 2011101620474 A CN2011101620474 A CN 2011101620474A CN 201110162047 A CN201110162047 A CN 201110162047A CN 102683578 A CN102683578 A CN 102683578A
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Abstract
The invention relates to a manufacturing method of a zinc oxide piezoelectric wire. A linear piezoelectric material consisting of a zinc oxide piezoelectric material is formed by the oxidation treatment on a zinc layer and the manufacture to a wire for leading-out a piezoelectric wire. The manufactured zinc oxide piezoelectric wire can be assembled in a bundling way.
Description
Affiliated technical field
The present invention relates to a kind of manufacturing approach that contains the wire rod of zinc oxide, the wire rod that this kind contains zinc oxide belongs to piezoelectric, can be used for captures energy, is a kind of new energy materials.
Background technology
At present, collecting wind energy and wave energy and scattered kinetic energy is an importance of new forms of energy and renewable energy resources research, and the development and application of piezoelectric newly relates to can large tracts of land, collect these energy whenever and wherever possible, has attracted the research effort of countries in the world.The research and development of zinc oxide piezoelectric enjoy attention because of its feature of environmental protection and relative cheapness property.The piezoelectric effect of zinc oxide nanowire can reach tens millivolts of voltages, electric current hundreds of nanoampere.If can realize making the series connection and the parallel connection of a large amount of zinc oxide nanowires technically; The series connection and the parallel connection of perhaps similar a large amount of zinc oxide (greater than nanoscale) line; Just can reach the charging requirement and the actual energy storage purpose of storage battery or super capacitor, make the energy that captures from nature to be used.
Summary of the invention
The object of the present invention is to provide a kind of manufacturing approach of zinc oxide piezoelectricity line, be used for high efficiency and collect wind energy and wave energy and various kinetic energy, reaching can be to the purpose of storage battery or super capacitor charging.The present invention is directed to the actual requirement of collecting wind energy and wave energy and various kinetic energy; Be that this type piezoelectric should have certain pliability, elasticity, huge high, the wiring of specific area, piezoelectricity efficient, easy for installation, durable, firm, can large-scale industrial production, cheap.The technical solution that the present invention proposes is directed against these requirements just.The present invention at first designs the utmost point of a kind of inner core lead (or being called conductive core) as this zinc oxide piezoelectricity line; The cross section of inner core lead can be circle, rectangle, perhaps special-shaped, and the conductive layer of the useful electrocondution slurry sintering of the material of selecting for use or conductive carbon fibre or conductive plastics or conductive rubber or electrically conductive graphite or grapheme material or copper or aluminium or tin or zinc or iron or silver or their alloy be the compound composition of these materials perhaps.In order to increase elasticity and flexibility, compound also can be the foaming shape.In order to gain in strength, can suitably add natural fiber or chemical fibre or glass fiber or mineral fibres or their braid and plastics or rubber in the compound.In order to make the material of selecting for use become compound, can add adhesive.Here the electrocondution slurry of indication is meant conductive silver paste or conducts electricity aluminium paste or conductive copper paste or the tin slurry or conduct electricity zinc slurry or conductive silver copper-clad slurry or conduct electricity aluminum paste or conductive carbon paste etc. of conducting electricity, and can add CNT, Graphene in the conductive carbon paste to increase electric conductivity and toughness.Then; On this inner core lead through chemical plating or electroplate or fusion plating or fusion evaporation plating or vacuum plating or these methods in several method; Plate layer of metal zinc, also can adopt the method for parcel zinc metal sheet or zinc wire perhaps to achieve the goal with the method for electrocondution slurry sintering last layer zinc metal sheet or zinc wire or the method for sintering conduction zinc slurry.Then; Through oxidizing process this layer metallic zinc is oxidized to zinc oxide; On zinc oxide film, form conductive layer again through the sintering electrocondution slurry; Perhaps adopt plating of chemical plating or vacuum or combination to electroplate or the method for fusion plating or coated metal or method or fusion pack or extrusion by melting or adhesive method and the formation of the several method in them conductive layer that the coated with conductive slurry adds the coated metal sintering; As another utmost point of this zinc oxide piezoelectricity line, the present invention is called outer conductive layers with this utmost point.And then with goods through high voltage polarization, last, the protectiveness rete is gone up in processing outside, generally can adopt plastic layer or rubber layer or organic coating layer, the present invention is called the outer protection layer with this skim layer.This zinc oxide piezoelectricity line itself can be processed into hundreds of and even go up km or longer; Can also carry out a large amount of series connection and parallel connection to enlarge its real area; Promptly can be assembled into one or boundling and be assembled into sheet or other shape, and then can export the voltage and current that meets storage battery or super capacitor charging requirement with many zinc oxide piezoelectricity line boundlings.When carrying out zinc oxide piezoelectricity line the boundling assembling; Can around zinc oxide piezoelectricity line, fill or encapsulate with elastomeric material; Purpose is to fill zinc oxide piezoelectricity line space on every side and protection zinc oxide piezoelectricity line; Can make the appropriateness distortion easily of zinc oxide piezoelectricity line again, the elastomeric material of being selected for use is carbon fiber or glass fiber or mineral fibres or chemical fibre or natural fiber or rubber or bipeltate or plastics or foamed plastic or their mixture.The pliability of zinc oxide piezoelectricity line and elasticity depend primarily on the pliability and the elasticity of inner core lead, depend on the outer field protective layer of piezoelectricity line in addition, and protective layer adopts has pliability and flexible materials processing to form.Generally; Can't Direct Electroplating or fusion plating on nonmetal; Therefore the present invention adopts chemical plating on zinc oxide film earlier, plates re-plating or fusion plating after the layer of metal, also can directly on zinc oxide film, carry out vacuum plating or sintering electrocondution slurry and form conductive layer.Therefore the energy output of the amount of the zinc oxide film that deposits on inner core lead decision zinc oxide piezoelectricity line can take on a conductive core repeatedly the method for depositing zinc oxide layer to make zinc oxide piezoelectricity line.When the deposition second layer and the above zinc oxide film of the second layer; Because the resistance of the zinc oxide film of internal layer can reduce the efficient of electroplating second layer metal zinc and the above metallic zinc of the second layer; Therefore can take the method plated metal zinc of plating of chemical plating or vacuum or fusion plating; The method that also can zinc metal sheet or zinc wire sintering be got on electrocondution slurry or the method for sintering conduction zinc slurry are transformed into zinc oxide film with oxidizing process then, deposit outer conductive layers again.According to the thickness of each layer zinc oxide film wherein, can be nano level, also can right and wrong nano level.Every deposition once oxidation zinc layer at least will be to the zinc oxide film processing that once polarizes, with the piezoelectricity efficient of effective raising zinc oxide piezoelectricity line.
The technical solution adopted for the present invention to solve the technical problems is: at first selecting has pliability and flexible conductive core wire rod, generally can select the conductive layer of conductive carbon fibre or conductive plastics or conductive rubber or electrically conductive graphite or Graphene or electrocondution slurry sintering formation or the compound of copper or aluminium or tin or zinc or iron or silver or their alloy and these materials to form.When forming compound, can add adhesive.When adopting zinc as conductive core, can on the zinc layer, directly form zinc oxide film, on the zinc layer, draw the utmost point of leading-out wire simultaneously as zinc oxide film.When adopting sintering conduction zinc slurry as conductive core, can after exposing the zinc layer with the polishing method on the conduction zinc slurry layer of sintering, be direct oxidation into zinc oxide film, simultaneously when sintering conduction zinc slurry the laying leading-out wire as a utmost point of zinc oxide film.For flexibility and the elasticity that increases the conductive core compound, when forming the conductive core compound, can add blowing agent and form foaming shape compound.In order to increase the intensity of conductive core compound, in composite material, can suitably add various natural fibers or chemical fibre or glass fiber or mineral fibres or their braid and plastics or rubber.Shape according to designing requirement decision cross section produces elastic conduction inner core lead, as a utmost point of zinc oxide piezoelectricity line.Conductive core can be hollow, also can be solid.Hollow conductive core mainly is to design for the thicker piezoelectricity line of section ratio.Conductive plastics and conductive rubber are meant the material that in plastics or rubber, adds metal or non-metallic conducting material, add manyly more, and electric conductivity is good more.In order to increase the self-supportive and the elasticity of zinc oxide piezoelectricity line; Can in the conductive core cavity, add certain elastic supporter, what the present invention adopted is plastics or rubber or carbon fiber or natural fiber or chemical fibre or glass fiber or mineral fibres or timber or bamboo wood material or their mixture or their braid or their compound or their expanded material.In order to carry out the compound of material, can select adhesive for use.For conductive core is hollow tubular, and the material of adding can be through inserting or fusion injection method or sicker injection method reach.The fusion injection method is injected in the conductive core cavity after being meant material crushed material (wherein thermoplastics will the be arranged) fusion that will join in the conductive core cavity.The sicker injection method is meant and adds a certain amount of adhesive in the crushed material of the material in needs join the conductive core cavity, is injected into then in the conductive core hollow pipe.If do not use hollow conductive core; Can be earlier on the elastic supporter material that increases the method through coated metal reach; Perhaps can combine again to electroplate or fusion is plated on the elastic supporter material of increase and forms conductive core with the plating of chemical plating or vacuum; Also can on the elastic supporter material that increases, form conductive core by the sintering electrocondution slurry, also can be on the elastic supporter material that increases through the coated with conductive slurry again the coated metal layer carry out sintering and form conductive core.In order to enhance productivity, also can the conductive core material to be attached to backing material with fusion pack or extrusion by melting or adhesive method and to get on.(use the fusion pack to be meant and in conductive core material powder or fiber, add a certain amount of thermoplastic macromolecule material, mix the back fusion, the method that forms integument is taken out in the elastic supporter material immersion back of need parcel.Extrusion by melting is meant and in conductive core material powder or fiber, adds a certain amount of thermoplastic macromolecule material, mixes the back and is wrapped in the conductive core that forms moulding on the elastic supporter material through melt extruding machine.The adhesive method is meant and in conductive core material powder or fiber, adds a certain amount of adhesive; With taking out after the immersion of elastic supporter material perhaps to extrude to be wrapping on the elastic supporter material or to inject mould molding the conductive core material is wrapping on the elastic supporter material through extruder; After the adhesive, conductive core is promptly plastic.) on the inner core lead, pass through chemical plating then or electroplate perhaps perhaps vacuum plating of fusion evaporation plating of perhaps fusion plating; Plate layer of metal zinc; Thickness can be in several nanometers to several millimeters; Also can will approach zinc metal sheet or zinc wire and be sintered on the conductive core or will approach zinc metal sheet or zinc wire directly is wrapping on the conductive core, also can on elastic supporter, form the zinc layer by sintering conduction zinc slurry with electrocondution slurry.Because metallic zinc need be through being oxidized into zinc oxide, blocked up coating is uneconomic for forming very thin zinc oxide film in its surface, is rational so metallic zinc thickness is chosen in several nanometers economically to several decimillimeters.The present invention has the method that the metallic zinc layer is oxidized to zinc oxide film more such: metallic zinc is carried out electrochemical anodization as anode; With metallic zinc heat treatment in 80～1000 ℃ of environment, bubbling air or also can feed oxygen enrichment or pure oxygen during heat treatment, when ambient temperature surpassed the melt temperature of metallic zinc, heat treatment period will shorten to that metallic zinc is only understood oxidation and can fusion; Carry out oxidation processes with chemical oxidizing agent, oxidant can be selected hydrogen peroxide solution; Handle with plasma generator and to make zinc generation oxidation generate zinc oxide.In normal temperature, its surface can form the basic zinc carbonate rete of the several atomic thickness of one deck very soon when metallic zinc generates, and the present invention is intended to make the basic zinc carbonate layer to be converted into zinc oxide film and the suitable zinc oxide film thickness that increases to the processing of zinc layer.In metallic zinc formed to zinc oxide grain, their arrangement not exclusively was the same, have vertical be tilted to, all angles horizontal growth is also arranged, through the HVDC electric polarization, can make arrangement consistent as far as possible, thereby increase piezoelectric effect.The zinc oxide surface that is exposed to the lead outermost is an other utmost point of piezoelectricity line, in order to connect external circuit, just must make conductive layer above that, and the present invention is called outer conductive layers.For pliability and the elasticity that increases the piezoelectricity line; The external conductive layer material that the present invention selects for use has sinter or copper or silver or aluminium or tin or zinc or iron or their alloy and their compound of conductive carbon fibre or conductive plastics or conductive rubber or electrically conductive graphite or Graphene or electrocondution slurry; Compound also can add blowing agent generation foaming shape when forming; Various natural fibers or chemical fibre or glass fiber or mineral fibres or their braid and plastics or rubber can be suitably added in the compound in order to increase the pliability and the elasticity of outer conductive layers, when adopting these materials, adhesive can be added.These material preparations to the method for zinc oxide surface are: through the method for chemical plating or vacuum plating; Earlier at zinc oxide surface deposition last layer conducting metal; Generally can be perhaps silver-colored or tin or zinc or aluminium (aluminium is not suitable for plating) of copper, can use electro-plating method on the basis of chemical plating or vacuum plating, to thicken the thickness of conducting metal for perhaps silver-colored perhaps tin of copper or zinc layer.Can use the method for the motlten metal that immerses them on the basis of chemical plating or vacuum plating, to thicken the thickness of conducting metal for tin or zinc layer.Also can directly adopt the method for fusion plating, for example with tin or zinc directly on zinc oxide film fusion form conductive layer.Also can adopt the method for sintering electrocondution slurry to form outer conductive layers.Also can adopt the method for parcel conducting metal or wrap up conducting metal combines the method for coated with conductive slurry sintering to form outer conductive layers.(the fusion pack is meant and in outer conductive layers material powder of selecting for use or fiber, adds a certain amount of thermoplastic macromolecule material also can to adopt fusion pack or extrusion by melting or adhesive method and the several method in them to form outer conductive layers; Mix the back fusion, the method that forms integument is taken out in the internal material immersion back of need parcel.Extrusion by melting is meant and in outer conductive layers material powder of selecting for use or fiber, adds a certain amount of thermoplastic macromolecule material, mixes the back and is wrapped in the outer conductive layers that forms moulding on the internal material through melt extruding machine.The adhesive method is meant and in outer conductive layers material powder of selecting for use or fiber, adds a certain amount of adhesive; Internal material is immersed that the back is taken out or extrudes the internal material that is wrapping on the internal material or will wrap up through extruder and put into also external conductive layer material crushed material and the adhesive selected for use of injection of mould; The demoulding after the adhesive, outer conductive layers are promptly plastic).When the zinc oxide skin selects for use electrocondution slurry sintering one deck conductive layer perhaps to add coated with conductive slurry sintering formation conductive layer with coated metal sheet or metal wire, when sintering, also can spread into external wire simultaneously.Externally on the conductive layer, can or adopt the sintering electrocondution slurry to overlay and connect external wire with contact method or welding into the method for lead.In order to play a protective role and pliability and elasticity to be arranged, can use the good plastics of weatherability or rubber or organic coating or their expanded material parcel at outermost layer, as shown in Figure 3.In order to increase the fastness of this protective layer, can in protective layer, add the combination mixture of glass fiber or carbon fiber or mineral fibres or chemical fibre or natural fiber or grapheme material or these materials.The outer protection layer material can adopt fusion pack or extrusion by melting or adhesive method and the several method in them to be formed on the outer conductive layers.Here the notion of the fusion pack of indication or extrusion by melting or adhesive method is with noted earlier identical.Because the energy output of the amount of the zinc oxide film that deposits on inner core lead decision zinc oxide piezoelectricity line, therefore can take on a lead repeatedly the method for depositing zinc oxide layer to make zinc oxide piezoelectricity line, shown in Fig. 2-1, Fig. 2-2.For on a lead, needing deposit multilayer zinc oxide film and this multilayer zinc oxide layer is under the situation of connecting; It also is the method for the conductive core of second layer zinc oxide film that internal structure can adopt the outer conductive layers of ground floor zinc oxide film, by that analogy, and shown in Fig. 2-1; Simultaneously for electroplating efficiency is improved; When electroplating second layer zinc layer, the negative electrode of plating can be connected on the outer conductive layers of ground floor zinc oxide film, by that analogy.The deposit multilayer zinc oxide film can realize that also multiple process connects, and sees instance 19, shown in Fig. 2-2 within it except portion is connected in series on a lead.In order to increase the reliability and the pliability of zinc oxide piezoelectricity line; The present invention has also designed the method that adds insulating barrier in the multilayer zinc oxide layer that can on a lead, deposit in addition; This method can be chosen in every alternating floor zinc oxide film and all add insulating barrier, sees instance 20, and is shown in figure 10; Also can optionally add the purpose of doing like this be the to try one's best interior resistance and the fastness of increase piezoelectricity line when distortion of each layer of balance zinc oxide piezoelectricity line.Every deposition once oxidation zinc layer, the processing that will once polarize at least, purpose is consistent as far as possible in order to reach the zincite crystal orientation, to improve the piezoelectricity efficient of device.The amount of the zinc oxide of handling when needs polarization can adopt direct current high voltage polarization method when fewer; Promptly (crystal grain is little in normal temperature to 300 ℃ scope; Temperature can be hanged down); On the two poles of the earth, apply the direct current (permission if equipment is had ready conditions, dc voltage can be higher) of 200～10,000 V/mm, the polarization time is about 1 second to 60 minutes.When the amount of the zinc oxide of handling when needs polarization is many,, therefore can adopt high-temperature low-pressure Direct current treatment method owing to need hundreds of thousands volt even higher high-tension apparatus; Temperature can be controlled at about 110～600 ℃; Apply the direct current of 5～100V/mm earlier, with the cooling extent cooling in per minute several years, on the basis of original direct voltage, progressively increase dc voltage simultaneously then; Increasing degree can reach about 500V/mm; When being cooled to ambient temperature again, withdraw from direct current, accomplish polarization and handle.
The invention has the beneficial effects as follows that the electric current that product of the present invention is produced reaches the voltage and current to the charging requirement of storage battery or super capacitor when being under pressure distortion.This product can be used in collects wind energy and wave energy and various lots of scattered kinetic energy aspect, and the product generating efficiency is high, the life-span is long, wiring, and is easy for installation, firm.Through adopting product of the present invention can be easy to be processed into final products, can large-scale industrial production, cheap, adaptable zone is vast, and strong impetus is played in energy-saving and emission-reduction.
Description of drawings
Fig. 1 is the piezoelectricity line schematic cross-section that has only one deck zinc oxide film.
Fig. 2-the 1st has the piezoelectricity line schematic cross-section (tandem type) of multilayer zinc oxide layer, and Fig. 2-the 2nd has the piezoelectricity line schematic cross-section (can connect or parallel connection type connects) of multilayer zinc oxide layer.
Fig. 3 is the zinc oxide piezoelectricity line schematic cross-section of hollow copper tubing as conductive core.
Fig. 4-the 1st, spring layer zinc oxide piezoelectricity line sketch map in the conductive core layer, Fig. 4-2 is a partial enlarged drawing.
Fig. 5 is the integrated blanket sketch map of piezoelectricity line that is processed into zinc oxide piezoelectricity line.
Fig. 6 is the zinc oxide piezoelectricity line sketch map of elastomeric support column in the conductive core layer, and the resiliency supported column section is circular, and wherein Fig. 6-1 is a front view, and Fig. 6-2 is a vertical view.
Fig. 7 is the zinc oxide piezoelectricity line sketch map of elastomeric support column in the conductive core layer, resiliency supported column section right and wrong circle, wherein Fig. 7-1 is a front view, Fig. 7-2 is a vertical view.
Fig. 8 is the schematic cross-section of round beaming type zinc oxide piezoelectricity line.
Fig. 9 is the schematic cross-section of platypelloid type beaming type zinc oxide piezoelectricity line.
Figure 10 is the schematic cross-section that between layer and layer, is added with the multilayer zinc oxide lamination electric wire of insulating barrier.
Embodiment
Instance one, get 0.3 millimeter of a diameter, long 300 millimeters anaerobic copper cash, see Fig. 1 (1),, see Fig. 1 (2) and (3) at the zinc layer of its electroplating surface one deck 0.02 millimeters thick as conductive core; Lead is put into 500 ℃ of baking ovens, slowly blast air, after 20 minutes, be cooled to normal temperature; Be warming up to 500 ℃ again and kept 20 minutes, be cooled to normal temperature, this moment, the copper conductor skin was the not oxidized zinc layer of one deck, saw Fig. 1 (2); The zinc layer is outward one deck zinc oxide film, sees Fig. 1 (3), on zinc oxide film, deposits one deck silver with chemical silver plating method, sees Fig. 1 (4); On silver layer, lay the anaerobic copper cash of 0.07 millimeter of a diameter, at this root copper cash and some conductive silver paste of silver layer contact position point, Fig. 1 (5) is seen in the cross section, puts into baking oven; Kept 30 minutes for 150 ℃, take out the cooling back, omits among Fig. 1, two copper cash heads of lead are connected 5 Kilovolt Direct Currents at outer coated with polyurethane protective layer; Be placed in 120 ℃ of silicone oil and polarized in 30 minutes, carry out the silicone oil cleaning after the polarization, make zinc oxide piezoelectricity line.
Instance two, on a conductive core, generate three layers of zinc oxide piezoelectric layer repeatedly, realize that series process connects three layers of zinc oxide piezoelectric layer, see Fig. 2-1; Wherein (1) is the utmost point of anaerobic copper cash conductive core as the piezoelectricity line, and (2) are not oxidized zinc layer, and (3) are zinc oxide film; (4) be oxygen-free copper layer with vacuum electroplating method deposition; (5) for the cross section behind anaerobic copper cash of laying on the outer oxygen-free copper layer and silver slurry sintering,, armor coated at skin again as an other utmost point of piezoelectricity line; Omit among Fig. 2-1, make zinc oxide piezoelectricity line.In this example, three layers of zinc oxide piezoelectric layer that generate on conductive core connect external circuit with series process, promptly are connected external circuit with the conductive core leading-out wire with outermost outer conductive layers leading-out wire.
Instance three, use long 0.6 meter a, external diameter be 15 millimeters, wall thickness be 1 millimeter hollow copper tubing as conductive core, the zinc layer of about 0.3 millimeter of fusion plating one deck on its extexine is put into pipe in 450 ℃ baking oven and was kept 1 hour; Then pipe is put into 150 ℃ baking oven, slowly fed pure oxygen, form zinc oxide film after 1 hour; Surperficial at it then with vacuum plated deposition layer of copper; The copper cash that outside winding is one 0.5 millimeter is as the leading-out wire of outer conductive layers, and coated with conductive copper is starched sintering, and processing then polarizes; And in copper pipe, insert the some about 2 millimeters bamboos of diameter and extremely fill up basically as the resiliency supported material that strengthens; Apply the plastic cement protective layer at skin, obtain zinc oxide piezoelectricity line, see Fig. 3.Wherein (1) is the conductive core of piezoelectricity line, and (2) are the zinc layer, and (3) are the zinc oxide film piezoelectric material layer; (4) being the copper layer, is outer conductive layers, and (5) are the bamboo fill area; (6) be piezoelectricity line plastic layer, (7) for connecting the leading-out wire of conductive core, (8) are the outer conductive layers leading-out wire.
Instance four, get 0.3 millimeter of a diameter, long 5 meters elastic wire, with the spring of 5 millimeters of its coiled internal diameters, at the copper of its electroplating surface one deck 0.05 millimeters thick, the zinc of re-plating one deck 0.02 millimeters thick; Put into 150 ℃ of baking ovens, slowly blast pure oxygen, after 30 minutes; Be cooled to normal temperature, this moment, outermost layer was one deck zinc oxide film, on zinc oxide film, deposited the silver layer of one deck 0.001 millimeter with electroless plating method; On this layer silver layer, electroplate the copper layer of 0.05 millimeter of one deck, connect leading-out wire again, with manufactured goods with the processing that polarizes of high-temperature low-pressure Direct current treatment method; At outer coated with polyurethane protective layer, processing inner core is the zinc oxide piezoelectricity line of spring, sees Fig. 4 again.
Instance five, get 1.5 millimeters of diameters, long 500 meters anaerobic copper cash,, put into 450 ℃ of baking ovens 30 minutes at the zinc of its surperficial continuous electroplating one deck 0.03 millimeters thick as the conductive core conductive core leading-out wire of holding concurrently; Slowly blast 40% oxygen enrichment then, after 10 minutes, be cooled to 150 ℃ and kept 15 minutes; Be cooled to normal temperature, this moment, the copper conductor skin was the not oxidized zinc layer of one deck, and the zinc layer is outward one deck zinc oxide film; On zinc oxide film, deposit the copper layer of 0.002 millimeter of one deck with the vacuum sputtering coating method, the anaerobic copper cash that on this layer copper layer, twines one 0.5 millimeter is starched at this root copper cash and copper layer contact position coated with conductive silver as the leading-out wire of outer conductive layers; Put into baking oven, kept 30 minutes, manufactured goods are polarized with the high-temperature low-pressure Direct current treatment for 150 ℃; Be specially elder generation manufactured goods are placed in the baking oven, temperature can be controlled at 400 ℃, keeps 20 minutes; On two electrodes, apply the direct current of 50V then, with the cooling extent cooling of per minute 5 degree, the while progressively increases dc voltage on the basis of the direct voltage of former 50V then; Increasing degree is about per minute 6V, rises near 500V in the clock time at 70 minutes, and is cooled to ambient temperature; Withdraw from direct current then, accomplish polarization and handle, at last at outer coated with polyurethane protective layer; Melt extrude machine in the external application of polyurethane protective layer again and apply thick 0.5 millimeter polyvinyl chloride insulation layer, process zinc oxide piezoelectricity line.
Instance six, get instance five manufactured goods, be cut into some of 50 millimeters long, separate the two poles of the earth, with it and be unified into carpet-like, see Fig. 5.Product can be used as the gentle breeze of pasting on the wall outside the building can catcher.
Instance seven, get 10 millimeters of diameters, long 3 meters elastic wire, become piezoelectric layer, see Fig. 6 in its Surface Machining; (1) is elastic wire; (2) be copper electrode, (3) are the zinc layer, and (4) are the zinc oxide piezoelectric layer; (5) be with conductive carbon paste sintering Copper Foil together as outer conductive layers, (6) polyurethane protective layer for applying.In this instance, the oxidation of zinc layer adopts plasma generation rifle that the zinc layer is carried out oxidation processes.
Instance eight, get a cross section for oval, major axis is 18 millimeters, and minor axis is 8 millimeters, long 3 meters a elastic wire; Become zinc oxide piezoelectric layer structure in its Surface Machining, see Fig. 7, (1) is elastic wire; (2) be copper electrode, (3) are the zinc layer, and (4) are the zinc oxide piezoelectric layer; (5) be with conductive carbon paste sintering Copper Foil together as outer conductive layers, (6) polyurethane protective layer for applying.
Instance nine, produce round beaming type piezoelectricity line, Fig. 8 is seen in the cross section.Being specially and getting external diameter is 3 millimeters, long 5 meters 7 on zinc oxide piezoelectricity line, and with 7 such piezoelectricity line parallels and assemble a branch ofly, outer packing protective layer, protective layer adopt glass fabric addition polymerization ammonia ester paint.(1) be single zinc oxide piezoelectricity line, (2) are the protective layer of outer parcel, and (3) are the foamed plastics fill area.
Instance ten, cut open and get platypelloid type beaming type zinc oxide piezoelectricity line, Fig. 9 is seen in the cross section.Being specially and getting external diameter is 5 millimeters, long 10 meters 29 on zinc oxide piezoelectricity line; With 29 such piezoelectricity line parallels and assemble a tabular; With the elastic caoutchouc encapsulation, outer packing protective layer, protective layer adopt glass fabric addition polymerization ammonia ester paint to wrap up the polyvinyl chloride insulation layer again.(1) be single zinc oxide piezoelectricity line, (2) are the protective layer of outer parcel, and encapsulation region is filled for elastic caoutchouc in (3).Such manufactured goods can be laid on road surface and be used for piezo-electric generating.
Instance 11, the lead that will be coated with the zinc layer immerse in 20% to 30% the hydrogen peroxide solution, and temperature is controlled at 30 to 40 ℃, and the time is 10 to 30 minutes, on the zinc layer, forms zinc oxide film.The lead that perhaps will be coated with the zinc layer immerses in 0.5% to 5% the hydrogen peroxide solution, and temperature is controlled at 50 to 80 ℃, and the time is 10 to 60 minutes, can on the zinc layer, form zinc oxide film.
Instance 12, conductive core are the zinc oxide piezoelectricity line instances of composite material.Select 15 millimeters of diameters for use; Long 3.5 meters nylon 66 poles; With its surperficial hacking; Lay the leading-out wire of the copper cash of 0.5 millimeter of a diameter along the length direction of nylon 66 poles, along the cross-wise direction of nylon 66 poles copper cash is tightened with copper wire with middle at the two ends of nylon 66 poles as conductive core.The conductivity type short carbon fiber of adding 0.5% in conductive copper paste; Conductive copper paste is coated on nylon 66 poles; The baking oven that nylon 66 poles are put into 130 ℃ was kept 20 minutes; Apply primary conductive copper slurry after the taking-up again, carry out same baking again, on nylon 66 poles, formed conductive core like this.The conductive core surface is polished with fine sandpaper, fully come out in the surface of outermost thin copper powder, rapidly nylon 66 poles were put into electroless zinc plating solution 5 minutes; Take out washing; 150 ℃ of baking ovens, slowly aerating oxygens are put in oven dry; Keep after 20 minutes and form zinc oxide film, take out.On the zinc oxide film that forms; Lay the leading-out wire of the copper cash of 0.5 millimeter of another root diameter along the length direction of nylon 66 poles as outer conductive layers; Tighten copper cash on the zinc oxide film surface along the cross-wise direction of nylon 66 poles with copper wire with middle at two ends at nylon 66 poles; Contain the conductive copper paste of 0.5% conductivity type short carbon fiber at zinc oxide film surface-coated secondary, put into 130 ℃ baking oven at every turn and kept 20 minutes, promptly form outer conductive layers.With the polarization of direct current high voltage polarization method, the polarization temperature is controlled at about 150 ℃ with manufactured goods.With plastic extruder externally on the conductive layer plastic cement of fusion parcel one deck 1.5 millimeters thick as outer protective layer.The goods of this instance can be used as wind energy and rock the generating goods.
Instance 13, inner elastomeric backing material are the zinc oxide piezoelectricity line instances of composite material.2 to 3 millimeters in cut-off footpath, long 4 meters many in bamboo are bundled into the about 30 millimeters boundling thing of diameter with cotton rope, are inserted in 33 millimeters of internal diameters, 3 millimeters of wall thickness, long 4 meters nylon 6 pipes, in the gap, inject two component silica gel and seal.With nylon tube surface hacking, lay the leading-out wire of the copper cash of 1 millimeter of a diameter along the length direction of nylon 6 pipes as conductive core, copper cash is tightened along the cross-wise direction of nylon 6 pipes with copper wire with middle at the two ends of nylon 6 pipes.The conductivity type short carbon fiber of adding 0.5% in conductive copper paste; Conductive copper paste is coated on nylon 6 pipes; The baking oven that nylon 6 pipes are put into 130 ℃ was kept 20 minutes; Apply primary conductive copper slurry after the taking-up again, carry out same baking again, on nylon 6 pipes, formed conductive core like this.The conductive core surface is polished with fine sandpaper, fully come out in the surface of outermost thin copper powder in the conductive copper paste sinter layer, rapidly nylon 6 pipes were put into electroless zinc plating solution 5 minutes; Take out washing; 150 ℃ of baking ovens, slowly aerating oxygens are put in oven dry; Keep after 20 minutes and form zinc oxide film, take out.On the zinc oxide film that forms; Lay the leading-out wire of the copper cash of 1 millimeter of another root diameter along the length direction of nylon 6 pipes as outer conductive layers; Tighten copper cash on the zinc oxide film surface along the cross-wise direction of nylon 6 pipes with copper wire with middle at two ends at nylon 6 pipes; At zinc oxide film surface-coated secondary conduction aluminium paste; Put into 130 ℃ baking oven at every turn and kept 20 minutes, promptly form outer conductive layers, with plastic extruder externally the polyurethane foam layer of fusion parcel one deck 3 millimeters thick on the conductive layer, again on the polyurethane foam layer plastic cement of fusion parcel one deck 1.5 millimeters thick as outer protective layer.With the polarization of direct current high voltage polarization method, the polarization temperature is controlled at about 120 ℃ with manufactured goods.The vertical installation of this instance can be used as wind-force and rocks TRT.
The zinc oxide piezoelectricity line of instance 14, use electroless zinc plating equipment is made instance continuously.Get the copper cash of 0.5 millimeter of sufficiently long diameter, make it, pass through sink after going out groove continuously through the electroless zinc plating groove; And slowly getting into continuous tunnel furnace (1), the temperature of continuous tunnel furnace (1) is controlled at 150 ℃, and feeds pure oxygen; Line point is 15 minutes through the time of continuous tunnel furnace (1), go out continuous tunnel furnace (1) after, along rectilinear direction and paste to twine the copper cash of 0.3 millimeter of a diameter; Coated with conductive copper is starched continuously above that, gets into continuous tunnel furnace (2) more simultaneously, and temperature is controlled at 130 ℃; Line point is 20 minutes through the time of continuous tunnel furnace (2), makes manufactured goods 1, with manufactured goods 1 around going into drum.Manufactured goods 1 are cut into per 30 meters one section, separate inside and outside leading-out wire, carry out polarizer with high-temperature low-pressure Direct current treatment method and get manufactured goods 2.With melt extruding nylon 6 insulating barriers of machine in manufactured goods 2 outerwrap 0.5 millimeters thick, melt extrude the polyvinyl chloride of machine parcel one deck 1 millimeters thick again in external application, process zinc oxide piezoelectricity line.In this instance; The copper cash that diameter is 0.5 millimeter is the conductive core conductive core leading-out wire of holding concurrently; The sinter layer that the conductive copper paste sintering forms is an outer conductive layers, and the copper cash that diameter is 0.3 millimeter is the leading-out wire of outer conductive layers, and nylon 6 insulating barriers and polyvinyl chloride insulation layer are the outer protection layers.
Instance 15, a kind of zinc oxide piezoelectricity line of fusion evaporation coating apparatus that uses are made instance continuously.Get the copper cash of 1.5 millimeters of sufficiently long diameters; Make it continuously through zinc fume coating equipment (fusion evaporation coating apparatus), in the zinc fume coating equipment with nitrogen or argon gas as protection gas, in graphite crucible, put into high-purity Zn; High-frequency induction heating to 550 is to 1000 ℃ of scopes; Make the high-purity Zn fusion and produce zinc fume, the surface is applied by zinc fume behind the copper cash process zinc fume coating equipment, forms even metal zinc layer through cooling surface.The copper cash that surfaces coated is covered with the zinc layer slowly gets into continuous tunnel furnace (1), and the temperature of continuous tunnel furnace (1) is controlled at 150 ℃, and feeds pure oxygen; Line point is 20 minutes through the time of continuous tunnel furnace (1), go out continuous tunnel furnace (1) after, along rectilinear direction and paste to twine the copper cash of 0.8 millimeter of a diameter; Coated with conductive copper is starched continuously again, then gets into continuous tunnel furnace (2), and temperature is controlled at 130 ℃; Line point is 30 minutes through the time of continuous tunnel furnace (2), makes manufactured goods 1, with manufactured goods 1 around going into drum.Manufactured goods 1 are cut into per 30 meters one section, separate inside and outside leading-out wire, carry out polarizer with high-temperature low-pressure Direct current treatment method and get manufactured goods 2.With melt extruding machine, process zinc oxide piezoelectricity line at the thick 1 millimeter polyvinyl chloride insulation layer of manufactured goods 2 outerwrap.In this instance; The copper cash that diameter is 1.5 millimeters is the conductive core conductive core leading-out wire of holding concurrently; The sinter layer that the conductive copper paste sintering forms is an outer conductive layers, and the copper cash that diameter is 0.8 millimeter is the leading-out wire of outer conductive layers, and the polyvinyl chloride insulation layer is the outer protection layer.
The zinc oxide piezoelectricity line of instance 16, use fusion coating apparatus is made instance continuously.Get the copper cash of 3 millimeters of sufficiently long diameters, make it, pass through sink after going out groove continuously through the electroless zinc plating groove; And get into oven for drying (during oven dry with nitrogen or argon gas as protection gas) rapidly, get into fusion coating apparatus (in graphite crucible, put into high-purity Zn, high-frequency induction heating to 500 is to 550 ℃ of scopes and with nitrogen or argon shield) more continuously; Slowly get into continuous tunnel furnace (1) more continuously, the temperature of continuous tunnel furnace (1) is controlled at 150 ℃, and feeds pure oxygen; Line point is 25 minutes through the time of continuous tunnel furnace (1), go out continuous tunnel furnace (1) after, cooled off 30 minutes; Get into a continuous tunnel furnace (1) again and carry out oxidation, condition is the same, goes out 0.5 millimeter of a diameter is twined in continuous tunnel furnace (1) back along rectilinear direction and subsides copper cash; Coated with conductive copper slurry gets into continuous tunnel furnace (2) again, and temperature is controlled at 130 ℃; Line point is 30 minutes through the time of continuous tunnel furnace (2), makes manufactured goods 1, with manufactured goods 1 around going into drum.Manufactured goods 1 are cut into per 30 meters one section, separate inside and outside leading-out wire, carry out polarizer with high-temperature low-pressure Direct current treatment method and get manufactured goods 2.With melt extruding the polyurathamc of foaming machine in manufactured goods 2 outerwrap 1.5 millimeters thick, melt extrude the polyvinyl chloride insulation layer of machine parcel one deck 1 millimeters thick again in the polyurathamc external application, process zinc oxide piezoelectricity line.
Instance 17, raw material adopt the manufacturing instance of zinc wire.The brass tube of getting 30 millimeters of external diameters, 1.5 millimeters of wall thickness, 3 meters of length is as conductive core.1 millimeter thick copper cash of a diameter of welding is as the conductive core leading-out wire on the brass tube top.Intensive around the zinc wire of going into 0.3 millimeter of one deck diameter on brass tube, apply one deck conduction zinc slurry above that, put it into baking oven, 130 ℃ were toasted 30 minutes; Take out the back and in dry atmosphere, surface finish is exposed zinc surface, put into baking oven then, slowly feed pure oxygen, keep to take out after 10 minutes being cooled to room temperature for 200 ℃; Placed 24 hours, and put into baking oven again, 200 ℃ of bakings; Slowly feed pure oxygen, take out after 20 minutes and be cooled to room temperature, form zinc oxide film; Again above that around the copper cash of going into 0.5 millimeter of one deck diameter as outer conductive layers and outer conductive layers leading-out wire, coated with conductive copper slurry puts it into baking oven above that; 130 ℃ were toasted 30 minutes, took out cooling, carried out primary conductive copper slurry again and handled.With the polarization of direct current high voltage polarization method, the polarization temperature is controlled at about 150 ℃ then.The fusion injection has added the backing material of nylon 6 plastics of staple glass fibre as conductive core in brass tube then.Melt extrude the polyurathamc that foaming machine wraps up 3 millimeters thick outside the using of goods at last, melt extrude the polyvinyl chloride insulation layer of machine parcel one deck 1.5 millimeters thick again in the polyurathamc external application, process zinc oxide piezoelectricity line.
Instance 18, stick with glue thing injection method and adhesive manufactured zinc oxide piezoelectricity line instance.In 30 millimeters of external diameters, wall thickness 3 millis, long 3 meters high temperature resistant ABS plastic, insert about 5 millimeters of diameter, mixture to the silica gel that in the space, injects two component silica gel and bamboo fibre solidifies to filling up basically for long 3 meters some in bamboo wood material, outside the ABS plastic pipe intensive around on the zinc wire of 0.3 millimeter of diameter be covered with whole surface; Zinc wire is fixed with screw at ABS plastic pipe two ends and connected the leading-out wire as conductive core with the copper cash of 1 millimeter of diameter; With plasma generation rifle zinc surface is handled, is made zinc surface be oxidized to zinc oxide, more above that with the copper cash of 0.3 millimeter of diameter around full whole surface; The two ends of 0.3 millimeter copper cash are fixed on the ABS plastic two ends with screw and connect the copper cash (outer conductive layers leading-out wire) of 1 millimeter of diameter; On 0.3 millimeter copper cash, apply one deck conductive copper paste, put it into baking oven, 120 ℃ were toasted 30 minutes; Take out; At the surperficial dip-coating ground floor outer protection layer of goods, composition is the mixture of two component silica gel and staple glass fibre and nylon 6 short fibers, after ground floor outer protection layer solidifies; Goods are with the polarization of direct current high voltage polarization method, and the polarization temperature is controlled at about 120 ℃.Wrap up one deck PEEK (polyether-ether-ketone) plastics as second layer outer protection layer at outermost layer with extrusion by melting again.Goods polarize with direct current high voltage polarization method again.Final zinc oxide piezoelectricity line manufactured goods can be used for the generating of rocking of wind-force.
Instance 19, produce a lead that 6 layers of zinc oxide piezoelectric material layer are arranged, see Fig. 2-2.Wherein (1) is the conductive core of ground floor, and (2) are the zinc layers, and (3) are the zinc oxide film piezoelectrics, and (4) are the outer conductive layers of the ground floor conductive core of the second layer of holding concurrently; (5) be the zinc layer, (6) are the zinc oxide film piezoelectrics, and (7) are the outer conductive layers of the second layer the 3rd layer the conductive core of holding concurrently, and (8) are the zinc layers; (9) be the zinc oxide film piezoelectric, (10) are the 3rd layer outer conductive layers the 4th layer the conductive core of holding concurrently, and (11) are the zinc layers; (12) be the zinc oxide film piezoelectric, (13) are the 4th layer the outer conductive layers conductive core of layer 5 of holding concurrently, and (14) are the zinc layers; (15) be the zinc oxide film piezoelectric, (16) are the outer conductive layers of the layer 5 conductive core of layer 6 of holding concurrently, and (17) are the zinc layers; (18) be the zinc oxide film piezoelectric, (19) are the outer conductive layers of layer 6, and (20) are the outer protection layers.If (1) and (20) as the leading-out wire of whole 6 layers zinc oxide piezoelectric lead, these 6 layers of zinc oxide piezoelectrics are to be in series connection.If (1), (7), (13), (19) are connected as a utmost point, (4), (10), (16) are connected as another utmost point, these 6 layers of zinc oxide piezoelectrics are to be in parallelly connected state.
Instance 20, produce the lead of the zinc oxide piezoelectric that haves three layers, each interlayer has insulating barrier to separate, and sees Figure 10.Wherein (1) is the conductive core of each layer, and (2) are the zinc layer of each layer, and (3) are the zinc oxide piezoelectric of each layer, and (4) are the outer conductive layers of each layer, and (5) are the insulating barrier of each layer.Such structure can make these 3 layers of zinc oxide piezoelectric material layers realize being connected in parallel.
Claims (10)
1. the manufacturing approach of a zinc oxide piezoelectricity line; It is characterized in that the piezoelectricity line manufactured mainly and be made up of conductive core, zinc layer, zinc oxide film piezoelectric, outer conductive layers, outer protection layer, it can be single piezoelectricity line, also can be the piezoelectricity line of boundling; Single piezoelectricity line inside can have only one deck zinc oxide piezoelectric material layer; Also the multilayer zinc oxide piezoelectric material layer can be arranged, the multilayer zinc oxide piezoelectric material layer adopts series process or multiple process to connect, and also can isolate with insulating barrier between each layer zinc oxide piezoelectric structure layer; The cross section of piezoelectricity line can be round, also can be other shape.
2. the conductive core of zinc oxide piezoelectricity line according to claim 1 is made up of the sinter of conductive carbon fibre or conductive plastics or conductive rubber or electrically conductive graphite or Graphene or electrocondution slurry or copper or aluminium or tin or zinc or iron or silver or their alloy and the compound of these materials; Compound also can be the foaming shape; Can add various natural fibers or chemical fibre or glass fiber or mineral fibres or their braid and plastics or rubber in the compound; When adopting these materials, can add adhesive; Conductive core can be solid also can be hollow; Conductive core can be linearity also can be curvilinear, the cross section of conductive core can be round, also can be other shape.
3. the conductive core of zinc oxide piezoelectricity line according to claim 2; Increase backing material in the cavities within it; The backing material that is adopted is plastics or rubber or carbon fiber or natural fiber or chemical fibre or glass fiber or mineral fibres or timber or bamboo wood material or their mixture or their braid or compound or their expanded material compound, when adopting these materials, can add adhesive.
4. when the conductive core of zinc oxide piezoelectricity line according to claim 3 increases backing material in the cavities within it; The material that increases can reach through method or the sicker injection method that hollow conductive core is injected in method or the fusion of inserting in the hollow conductive core; Also can the method through coated metal reach in the backing material outside that increases; Perhaps can combine again to electroplate or fusion is plated on the backing material of increase and forms conductive core with the plating of chemical plating or vacuum; Also can on the backing material that increases, form conductive core by the sintering electrocondution slurry; Also can be on the backing material that increases through the coated with conductive slurry again coated metal carry out sintering and form conductive core, also can the conductive core material be attached to backing material with fusion pack or extrusion by melting or adhesive method and the several method in them and get on.
5. the zinc oxide film piezoelectric of zinc oxide piezoelectricity line according to claim 1 is on conductive core, to form the zinc layer through elder generation, and then is oxidized to zinc oxide, forms through the hyperpolarization processing again.
6. the zinc layer of zinc oxide piezoelectricity line according to claim 5 is with electroplating or chemical plating or fusion plating or fusion evaporation plating or vacuum plating or their combined method; And the method for sintering conduction zinc slurry; And the formation of the method for parcel zinc metal sheet and zinc wire, also can adopt electrocondution slurry to carry out sinter bonded when parcel zinc metal sheet and zinc wire.
7. the oxidation of the zinc layer of zinc oxide piezoelectricity line according to claim 5 is with air oxidation process or oxygen-rich oxide method or pure oxygen oxidizing process or metallic zinc is carried out electrochemical anodization or hydrogen peroxide oxidation method or plasma oxidation method as anode form.
8. the electric conducting material that the outer conductive layers of zinc oxide piezoelectricity line according to claim 1 adopts is sinter or copper or aluminium or tin or zinc or iron or silver or their alloy and their compound of conductive carbon fibre or conductive plastics or conductive rubber or electrically conductive graphite or Graphene or electrocondution slurry; Compound also can be the foaming shape; Various natural fibers or chemical fibre or glass fiber or mineral fibres or their braid and plastics or rubber can be added in the compound, when adopting these materials, adhesive can be added.
9. the outer conductive layers of zinc oxide piezoelectricity line according to claim 1 is to use through sintering electrocondution slurry or chemical plating or vacuum plating or electroplate or the method for fusion plating or coated metal or method that the coated with conductive slurry adds the coated metal sintering or fusion pack or extrusion by melting or adhesive method and the several method in them form.
10. the outer protection layer of zinc oxide piezoelectricity line according to claim 1 is made up of the dry thing of plastics or rubber or organic coating; Also can adopt the dry thing of foamed plastic or bipeltate or organic foamed coating to constitute; And the constituting of these materials; The combination mixture that can add carbon fiber or glass fiber or mineral fibres or chemical fibre or natural fiber or Graphene or these materials in plastics or rubber or the organic coating; Adopt fusion pack or extrusion by melting or adhesive method and the several method in them to be formed on the outer conductive layers; When zinc oxide piezoelectricity line boundling assembles; Space between the piezoelectricity line can with carbon fiber or glass fiber or mineral fibres or chemical fibre or natural fiber or rubber or bipeltate or plastics or foamed plastic or their mixture be filled or encapsulation, adopts fusion pack or extrusion by melting or adhesive method and the several method in them when filling or encapsulating.
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| WO2014048038A1 (en) * | 2012-09-28 | 2014-04-03 | 中国电力科学研究院 | Conducting wire based on graphene nanomaterial |
| CN103811654A (en) * | 2012-11-15 | 2014-05-21 | 纳米新能源（唐山）有限责任公司 | Piezoelectric cable having piezoelectric effect and manufacturing method and application thereof |
| CN112289487A (en) * | 2020-09-25 | 2021-01-29 | 无锡光美新能源科技有限公司 | Novel high-temperature-resistant flame-retardant high-conductivity electric vehicle wire harness and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1707934A (en) * | 2004-06-10 | 2005-12-14 | 米其林技术公司 | Piezoelectric ceramic fibers having metallic cores |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1707934A (en) * | 2004-06-10 | 2005-12-14 | 米其林技术公司 | Piezoelectric ceramic fibers having metallic cores |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014048038A1 (en) * | 2012-09-28 | 2014-04-03 | 中国电力科学研究院 | Conducting wire based on graphene nanomaterial |
| CN103811654A (en) * | 2012-11-15 | 2014-05-21 | 纳米新能源（唐山）有限责任公司 | Piezoelectric cable having piezoelectric effect and manufacturing method and application thereof |
| CN103811654B (en) * | 2012-11-15 | 2017-03-08 | 纳米新能源（唐山）有限责任公司 | There is piezoelectric cable of piezoelectric effect and its production and use |
| CN112289487A (en) * | 2020-09-25 | 2021-01-29 | 无锡光美新能源科技有限公司 | Novel high-temperature-resistant flame-retardant high-conductivity electric vehicle wire harness and preparation method thereof |
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| Publication number | Publication date |
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| CN102683578B (en) | 2015-02-25 |
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