CN103516255B - Integrated nanometer generator and preparation method thereof - Google Patents
Integrated nanometer generator and preparation method thereof Download PDFInfo
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- CN103516255B CN103516255B CN201210199363.3A CN201210199363A CN103516255B CN 103516255 B CN103516255 B CN 103516255B CN 201210199363 A CN201210199363 A CN 201210199363A CN 103516255 B CN103516255 B CN 103516255B
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Abstract
A kind of integrated nanometer generator and preparation method thereof.Described integrated nanometer generator is parallel integrated on the large-area metal level being covered with sand grains by least two series connection integrated unit M; Described series connection integrated unit M is connecting integrated by least two nano generators perpendicular to metal level direction.The preparation method of this integrated nanometer generator comprises: be ejected into respectively by sand grains on a face of metal level, obtains the metal level that one face is covered with sand grains.Present invention enhances hydrophily and the durability of metal level substrate, make it possible to parallel in this substrate that homoepitaxial has nano zine oxide, series connection nano generator, obtain integrated nano generator.
Description
Technical field
The present invention relates to a kind of nano generator, especially relate to a kind of nano generator that parallel series nano generator unit is integrated in large-area metal substrate.
Background technology
2006, mechanical energy was successfully converted to electric energy by georgia ,u.s.a Institute of Technology professor Wang Zhonglin etc. within the scope of nanoscale, develops generator-nano generator minimum in the world.But, although developed single nano generator, its power limited, a large amount of nano generator co-operation must have been had, form a generating set, really could meet the actual needs used.
Due to energy crisis and global warming, the emphasis of research is at present: the resource of seeking alternative energy source, the renewable energy resources based on such as daylight, wind, hydrogen or geothermal resources and green energy resource.Prior art has the energy harvesting technology based on these natural resourcess, and the use of these technology is also increasing gradually.But, in our living environment, still have the energy resource of many forms not to be utilized.Source of mechanical energy is one of most representative resource, can vibration, mankind's walking, moving vehicle etc. sufficient from living environment artificially generate, but these resources has been wasted usually.
The general principle of nano generator is: when nano wire (NWs) during dynamic tensile, generates piezoelectricity electromotive force under external force in nano wire, and corresponding transient current flows at two ends to balance Fermi level.Existing nano generator and nanometer generating unit, due to high cost, low output procedure and weak durability, be difficult to be applied to energy harvesting device and extract mechanical energy from environment.
Summary of the invention
Technical problem to be solved by this invention is: the defect overcoming the high and low output procedure of existing nano generator cost and weak durability, a kind of integrated nanometer generator is provided, have in the large area sandblasted metal substrate of zinc oxide nanowire at homoepitaxial, parallel series integrated nanometer generator, this nano generator cost benefit is high, output current and voltage performance high, the mechanical movement of the mankind and automobile can be changed into electricity.
Integrated nanometer generator of the present invention, adopt the large-area metallic substrates being covered with sand grains, there is hydrophily and the durability of enhancing, zinc oxide nanowire (NWs) can homoepitaxial in this large-area metal substrate, this metallic substrates is used as bottom electrode, for parallel, series connection integrated nanometer generator provide the foundation.The present invention is by top electrode level and/or vertically separate, and is all connected respectively on top electrodes by every root wire, Horizontal collection nano generator, to strengthen output current.Growth outside bottom electrode has the large-area metal substrate of zinc oxide nanowire to be divided into nano generator by the present invention, and by these generator vertically pilings, series connection integrated nanometer generator, to strengthen output voltage.
In order to solve the problems of the technologies described above, the first technical scheme provided by the invention is, a kind of integrated nanometer generator, parallel integrated on the large-area metal level being covered with sand grains by least two series connection integrated unit M; Described series connection integrated unit M is connecting integrated by least two nano generators perpendicular to metal level direction; Described nano generator comprises: lower electrode layer, zinc oxide nano-wire array, polymeric dielectric layer and upper electrode layer, described zinc oxide nano-wire array vertical-growth is on lower electrode layer, described zinc oxide nano-wire array is coated with described polymeric dielectric layer, described zinc oxide nano-wire array covers by described polymeric dielectric layer, and described upper electrode layer is arranged on polymeric dielectric layer.
Aforesaid integrated nanometer generator, in described series winding integrated unit M, the bottom electrode at upper nano generator is used as at the top electrode of lower nano generator, described electrode is gold, silver, platinum, aluminium, nickel, copper, titanium, iron, any one in selenium or their alloy, preferred aluminium, the surface of its growth of zinc oxide nano linear array is covered with sand grains.
Aforesaid integrated nanometer generator, the particle diameter of described sand grains is 30-70 μm, preferred 45-55 μm.
Aforesaid integrated nanometer generator, described series connection integrated unit M is 2-500, and in each series connection integrated unit M, nano generator is 2-500.
Aforesaid integrated nanometer generator, described series connection integrated unit M is 5-25, and in each series connection integrated unit M, nano generator is 3 to 20.
Aforesaid integrated nanometer generator, described polymeric dielectric layer is polymethyl methacrylate or dimethyl silicone polymer
Aforesaid integrated nanometer generator, described metal level is gold, silver, platinum, aluminium, nickel, copper, titanium, iron, any one in selenium or its alloy, preferred aluminium.
Aforesaid integrated nanometer generator, described Seed Layer is zinc oxide seed layer or gold seeds layer.
Second technical scheme provided by the invention is, a kind of preparation method of integrated nanometer generator, and the method comprises the steps: that sand grains is ejected on a surface of metal level by a., obtains the metal level that one face is covered with sand grains; B. in the metal level being covered with sand grains, form Seed Layer, vertical-growth zinc oxide nano-wire array in the Seed Layer of metal level, then, by spin-coating method, polymeric dielectric layer is covered on zinc oxide nano-wire array layer; C. at least step a and b is repeated once; D. using one of them in gained metal level as bottom electrode, these all the other metal levels be used as outside bottom electrode are divided at least two unit respectively, then described unit are stacked on bottom electrode, form at least double-layer structure body; E. on each nano generator of top layer, place top electrode metal layer respectively, obtain integrated nanometer generator.
Preferred top electrodes for being selected from gold, silver, platinum, aluminium, nickel, copper, titanium, iron, a kind of in selenium or its alloy.
The sand grains pressure of average grain diameter 30-70 μm (preferably 50 μm), in step a, is 3.5-4.5 kilogram/cm by the preparation method of aforesaid integrated nanometer generator
2(preferably 4 kilograms/cm
2) blast injection to aluminium lamination surface.
The preparation method of aforesaid integrated nanometer generator, in stepb, on the seed layer after growth of zinc oxide nano linear array, by metal level leaching 70-120 second (preferably 90 seconds) in diallyl dimethyl ammoniumchloride (PDADMAC) solution and poly (sodium 4-styrenesulfonate) (PSS) respectively.
The preparation method of aforesaid integrated nanometer generator, in stepb, described Seed Layer is zinc oxide seed layer.
Accompanying drawing explanation
Fig. 1 is parallel, the series connection diagram of integrated nanometer generator of the present invention;
Fig. 2 (a) is nano generator schematic diagram; Fig. 2 (b) is the Flied emission scanning electron microscopy of the zinc oxide nanowire of dense growth on the aluminium lamination substrate surface after blasting treatment;
Fig. 3 is at the not endurance test result scanning electron microscopy of growth of zinc oxide nano line in the smooth aluminium lamination substrate of blasting treatment;
Fig. 4 is the endurance test result scanning electron microscopy of growth of zinc oxide nano line in the aluminium lamination substrate through blasting treatment;
Fig. 5 (a) is integrated nanometer generator model schematic diagram; Fig. 5 (b)-(d) is this integrated nanometer generator model integrated electric flow graph; The integrated voltage pattern of this integrated nanometer generator model of Fig. 5 (e);
Fig. 6 is running after 20 hours, Fig. 5 nano generator MODEL C
2the output voltage figure of part;
Fig. 7 improves from 2-8Hz with driving frequency, Fig. 5 nano generator MODEL C
2the output voltage figure of part;
Fig. 8 is the voltage and current figure that parallel series integrated nanometer generator obtains in mankind's walking.
Embodiment
For fully understanding the object of the present invention, feature and effect, by following concrete execution mode, the present invention is elaborated.
Integrated nanometer generator of the present invention, zinc oxide nanowire (NWs) homoepitaxial is covered with in the metallic substrates of sand grains large-area, and growth zinc oxide nanowire on this substrate demonstrates fabulous durability under external force.As shown in Figure 1, because all primary zinc oxide nanowires are evenly connected in metallic substrates, substrate becomes the bottom electrode of integrated nanometer generator.In order to parallel integrated nano generator, by top electrode horizontal and vertical separately, and every root wire is all connected respectively on electrode.In order to integrated nanometer generator of connecting, the large-area metal substrate of zinc oxide nanowire there is is to be divided into nano generator the growth except being used as bottom electrode, and by these generator vertically pilings.The top electrode of lower nano generator is used as the bottom electrode of upper nano generator.In conjunction with above-mentioned parallel, series connection method, obtain parallel and integrated nano generator of connecting.
A kind of integrated nanometer generator, parallel integrated on the large-area metal level being covered with sand grains by least two series connection integrated unit M; Described series connection integrated unit M is connecting integrated by least two nano generators perpendicular to metal level direction; As shown in Figure 2 (a) shows, each nano generator comprises: lower electrode layer, zinc oxide nano-wire array, polymeric dielectric layer and upper electrode layer, described zinc oxide nano-wire array vertical-growth is on lower electrode layer, described zinc oxide nano-wire array is coated with described polymeric dielectric layer, and described zinc oxide nano-wire array covers by described polymeric dielectric layer, and described upper electrode layer is arranged on polymeric dielectric layer.
In the present invention, the nano generator integrated morphology of described integrated nanometer generator is: nano generator, perpendicular to the series connection of metal level direction, forms series connection integrated unit M; M is integrated at the plane in parallel perpendicular to metal level direction for series connection integrated unit, forms integrated nanometer generator of the present invention.
This integrated nanometer generator is made up of following method, is ejected into by sand grains on a surface of metal level, obtains the metal level that one face is covered with sand grains; B. in the metal level being covered with sand grains, form Seed Layer, vertical-growth zinc oxide nano-wire array in the Seed Layer of metal level, then, by spin-coating method, polymeric dielectric layer is covered on zinc oxide nano-wire array layer; C. at least step a and b is repeated once; D. using one of them in gained metal level as bottom electrode, these all the other metal levels be used as outside bottom electrode are divided at least two unit respectively, then described unit are stacked on bottom electrode, form at least double-layer structure body; E. on each nano generator of top layer, place top electrode metal layer respectively, obtain integrated nanometer generator.
Rotary coating polymeric dielectric layer on the face having zinc oxide nanowire in the growth of metal level, described polymeric dielectric layer is polymethyl methacrylate or dimethyl silicone polymer, preferred polymethyl methacrylate (PMMA).The thickness of the present invention to polymeric dielectric layer does not have particular/special requirement, can play in the thickness range of insulating effect, preferably thin polymeric layer, such as rotary coating thickness 1.5-2.5 μm of (more preferably 2 μm) polymethyl methacrylate layers.
Owing to have employed polymeric dielectric layer, the existence of insulating barrier provides the potential barrier of an infinite height, stops the piezoelectron on zinc oxide nanowire to be derived by zinc oxide/inside, Metal Contact face, and forms piezoelectric field; Piezoelectric field forms charge inducing at top electrode and bottom electrode further, and charge inducing forms current circuit when external circuits is connected.Polymeric dielectric layer forms cover layer on nano wire, and when vertically applying external force, stress can be sent to the nano wire under all force regions by cover layer, greatly improve the efficiency of nano generator; Cover layer is also coated on nano-wire array top and surrounding simultaneously, plays cushioning effect to a certain extent, and enhances the contact of nano-wire array and lower electrode layer, thus improve the stability of nano generator when nano wire bears External Force Acting.
As shown in Figure 5, the maximum output voltage of the series connection integrated unit M that the series connection of 3 nano generators is formed reaches 0.43V, and adopts 3 such series connection integrated unit M parallel integrated, and maximum output current reaches 102nA.And the three-dimensional integrated nanometer generator be made up of width, length and height three units respectively shows the potential as energy harvesting device under the mankind walk; As shown in Figure 8, maximum output voltage is more than 3V, and maximum output current reaches 195nA.
The present inventor finds through research: the hydrophily of reinforcement metal layer substrate and durability, zinc oxide nanowire just can be made to grow at its surface uniform, obtain the large-area metal layer substrate of growth of zinc oxide nano line, and then can on this substrate parallel, series connection nano generator, obtain integrated nano generator.
In order to strengthen the hydrophily of metal level substrate, enable zinc oxide nanowire at its surface homoepitaxial, and stop zinc oxide nanowire to be separated from metal level substrate at interface under external tension, before zinc oxide nanowire growth, preliminary treatment is carried out to metal level substrate, its surface is made to be covered with sand grains, to increase the contact surface area with zinc oxide nanowire.
Metal level substrate can be gold, silver, platinum, aluminium, nickel, copper, titanium, iron, any one in selenium or their alloy, preferred aluminium foil.Because aluminium has high performance-price ratio and light weight, its be not only a fabulous electric conductor and also be quality can not demote can recycled materials.In the present invention special requirement be there is no to the thickness of aluminium foil, aluminum foil thickness of the present invention can be implemented all within protection scope of the present invention.The preferred purity more than 99.0% (preferably more than 99.5%) of the present invention, the preferred 0.1mm of thickness 0.08-0.12mm() industrial aluminium foil as electrode and substrate.Zinc oxide nanowire only grows in the one side of metal level (aluminium foil), and therefore the another side of metal level (aluminium foil) can be used as the top electrode of the nano generator be connected on below.
Preferably, the preprocess method of metal level substrate is for carry out blasting treatment to metal level substrate.Being specially, is 3.5-4.5 kilogram/cm by the sand grains pressure of average grain diameter 30-70 μm (preferred 45-55 μm, more preferably 50 μm)
2(preferably 4 kilograms/cm
2) blast injection on a face of metal, produce microroughness on the metal surface, then use the substrate of deionized water rinsing sandblasted metal.Grow in metal level substrate to enable zinc oxide nanowire; need the metal level substrate surface after blasting treatment generates Seed Layer; the method generating Seed Layer is this area conventional method; special requirement is not had to the thickness of Seed Layer yet, seed layer thickness of the present invention can be implemented all within protection scope of the present invention.Such as adopt sputter on aluminium lamination substrate surface, generate a preferred 100nm of thickness 50-150nm() zinc oxide seed layer.
The present invention adopts conventional chemical growing method, and zinc oxide nanowire is grown at the metal level substrate surface with Seed Layer, such as adopt 0.1mol/L concentration by equimolar urotropine (HMTA) and zinc nitrate hexahydrate (ZnNO
3.6 (H
2o) nutrient solution) formed, faces down aluminium substrate one and is placed on nutrient solution top, and at 85 DEG C, grow 16 hours, the size of primary zinc oxide nanowire is approximately diameter 100-200nm, length about 2 μm.
In the past, in zinc oxide nanowire growth course, the bubble produced in nutrient solution rises to solution surface and is often caught by ventricumbent substrate surface, inhibits zinc oxide nanowire homoepitaxial on large-area metal layer substrate surface.
In the present invention, owing to having carried out blasting treatment to metal level substrate, enhance roughness and the surface oxidation of metal level substrate surface, the metal level substrate surface after blasting treatment shows the hydrophily of enhancing.Therefore, in zinc oxide nanowire growth course, the bubble metal level substrate surface produced in nutrient solution, zinc oxide nanowire is homoepitaxial on large-area metal layer substrate surface.It is the Flied emission scanning electron microscopy (FE-SEM) of the zinc oxide nanowire of dense growth on the aluminium lamination substrate surface after blasting treatment shown in Fig. 2 (b).
In the present invention, owing to having carried out blasting treatment to metal level substrate, grow and demonstrated fabulous durability under external force at the suprabasil zinc oxide nanowire of metal level.In the past, at not growth of zinc oxide nano line in the smooth aluminium lamination substrate of blasting treatment, when these samples under external force, such as bend, because zinc oxide and flexible substrates exist tension difference on interface, zinc oxide nanowire is easy to be separated from substrate.At the not endurance test result scanning electron microscopy of growth of zinc oxide nano line in the smooth aluminium lamination substrate of blasting treatment shown in Fig. 3.Prepare 3mm bending radius at the not sample of growth of zinc oxide nano line in the smooth aluminium lamination substrate of blasting treatment, by ballpoint pen by curling for this sample, as can be seen from (a) and (b) of Fig. 3, zinc oxide film, comprises Seed Layer and zinc oxide nanowire all comes off from smooth aluminium lamination substrate.It is the endurance test result scanning electron microscopy of growth of zinc oxide nano line in the aluminium lamination substrate through blasting treatment of the present invention shown in Fig. 4 b.Preparing the sample of growth of zinc oxide nano line in the aluminium lamination substrate through blasting treatment of 3mm bending radius, by ballpoint pen by curling for this sample, is the scanning electron microscopy amplified in the circular and rectangular broken line of Fig. 4 b shown in Fig. 4 c and 4d respectively.Although find there are some crackles (marking with arrow) in Fig. 4 c, there is not the region that zinc oxide nanowire is stripped aluminium lamination substrate.And as shown in figure 4d, near the edge of scissors cut, zinc oxide nanowire is also firmly attached in substrate.As can be seen from foregoing, because the contact surface area increased causes good bond between metal level substrate and zinc oxide nanowire two surfaces.In addition, when metal level substrate bends, the exterior surface area of increase also may reduce the surface tension of metal level substrate, thus can reduce the tension force difference of zinc oxide (comprising Seed Layer and nano wire) and substrate interface.Generally speaking, grow and demonstrate fabulous durability under external force at the suprabasil zinc oxide nanowire of the metal level of microroughness.
Due to homoepitaxial in zinc oxide nanowire to have microroughness metal level substrate in large area, and metal level substrate is applied as upper/lower electrode simultaneously, the nano generator based on metal level substrate can parallel series be integrated increases output voltage and electric current.It is schematic diagram that is parallel, the three-dimensional integrated nano generator of series connection shown in Fig. 1.The present invention is growth of zinc oxide nano line in the large-area one side with the metal level substrate of microroughness, does not have the basal surface of growth of zinc oxide nano line as bottom electrode, and this bottom electrode connects a wire.In order to parallel integrated nano generator, top electrode layer horizontal and vertical is separated, and every root wire is all connected respectively on each top electrodes separated.In order to integrated nanometer generator of connecting, the large-area metal layer substrate of zinc oxide nanowire there is is to be divided into nano generator the growth except being used as bottom electrode, and by these unit vertical pile.The top electrode of lower nano generator is used as the bottom electrode of upper nano generator.In conjunction with above-mentioned parallel, series connection method, obtain parallel and integrated nano generator of connecting.
Nano generator based on metallic substrates of the present invention is not only easy to parallel integrated to obtain not by the High Output Current of size restrictions, and is easy to integrated acquisition high output voltage of connecting.Illustrate the preparation method of integrated nanometer generator of the present invention below.
Be 3.5-4.5 kilogram/cm by the sand grains pressure of average grain diameter 30-70 μm (preferably 50 μm)
2(preferably 4 kilograms/cm
2) blast injection on a face of metal (preferred aluminium), be covered with sand grains on the metal surface, then use the substrate of deionized water rinsing sandblasted metal.Adopt sputter on the face of blasting treatment, generate the zinc oxide seed layer of a thickness 50-150nm (preferred 100nm) in metal level substrate.
Adopt 0.1mol/L concentration by equimolar urotropine (HMTA) and zinc nitrate hexahydrate (ZnNO
36 (H
2o) nutrient solution) formed, has facing down of zinc oxide seed layer to be placed on nutrient solution top by the generation of metallic substrates, at 85 DEG C, grow 16 hours, the size of primary zinc oxide nanowire is approximately diameter 100-200nm, length about 2 μm.There is the metallic substrates of zinc oxide nanowire also dry in atmosphere with deionized water rinsing growth.
Metallic substrates is soaked 70-120 second (90 seconds), respectively with preliminary treatment zinc oxide nanowire in diallyl dimethyl ammoniumchloride (PDADMAC) solution and poly (sodium 4-styrenesulfonate) (PSS).
This metallic substrates is used as the bottom electrode (bottom) of device, then the polymeric layer (polymethyl methacrylate (PMMA) layer) of rotary coating thickness 1.5-2.5 μm (preferably 2 μm) on the face having zinc oxide nanowire at this substrate grown, the face not having growth of zinc oxide nano line connects a wire.
Repeat the process of the above-mentioned line of growth of zinc oxide nano on the metallic substrate, the number of nano generator in series winding nano generator M as required, determine the number needing the substrate prepared.Each metallic substrates is cut into respectively size (0.9-1.3) × (1.2-1.6) cm
2(preferably 1.1 × 1.4cm
2) unit.Each unit is overlayed on bottom (bottom electrode-baseplate), form at least double-layer structure body, and fix with the edge of Kapton Tape by each unit.Each nano generator of top layer places top electrode metal layer respectively, and is connected with each top electrodes with wire respectively.
The structural formula of the present invention's diallyl dimethyl ammoniumchloride used (PDADMAC) is as follows
The structural formula of the present invention's poly (sodium 4-styrenesulfonate) used (PSS) is as follows
The structural formula of the present invention's polymethyl methacrylate used (PMMA) is as follows
In order to study the possibility that integrated nanometer generator of the present invention expands, the integrated unit M parallel integrated number of namely connecting, and the number of nano generator in each series connection integrated unit M, establish the integrated nanometer generator as drag.As shown in Fig. 5 (a), this integrated nanometer generator comprises 9 series connection integrated unit M, i.e. a
1, a
2, a
3, b
1, b
2, b
3, c
1, c
2, c
3, wherein connect integrated unit a
1, a
2and a
3the number of middle nano generator is respectively 1, b
1, b
2and b
3the number of middle nano generator is respectively 2, c
1, c
2and c
3the number of middle nano generator is respectively 3.Above-mentioned 9 series connection integrated unit M are parallel integrated on the metal layer, obtain the integrated nanometer generator as shown in Fig. 5 (a).The output signal of this nano generator is recorded with low noise voltage preamplifier (research on standard device, model SR560) and low noise electric current and voltage preamplifier (research on standard system model SR570).With trigger, such as sinusoidal servo controller (LabworksInc. company, model SC-121) and linear power amplifier (LabworksInc. company, model PA-119) put this integrated nanometer generator with the frequency period of 2Hz according to defeating of 100N.In order to ensure each part measuring integrated nano generator under the same conditions, meet following standard with the trigger that integrated nanometer generator contacts: each part of integrated nanometer generator adopts same material and identical contact area.(such as a is tested when measuring the output current of series connection integrated unit component N (parallel integrated by three series connection integrated unit M)
1, a
2, a
3parallel integrated electric current superposition), in order to the tension force providing phase same level to integrated nanometer generator, applied force is almost that test one series connection integrated unit M(such as only tests a
1or a
2or a
3) three times of power.As shown in Fig. 5 (b), test 3 series connection integrated unit a respectively
1, a
2, a
3, the output current of display 12,22 and 16nA, and when these 3 series connection integrated units are parallel integrated, obtain the output current of a 42nA.As shown in Fig. 5 (c), 3 series connection integrated unit b
1, b
2, b
3(in each series connection integrated unit, nano generator number is 2) is parallel integrated, obtains the output current of a 69nA; As shown in Fig. 5 (d), 3 series connection integrated unit c
1, c
2, c
3(in each series connection integrated unit, nano generator number is 3) is parallel integrated, obtains the output current of a 102nA.As shown in Figure 5, although the magnitude of current that the parallel integrated nano generator measured exports slightly is less than the sum of indivedual output current, but result shown in Fig. 5 demonstrates and parallelly in the large-area metallic substrates being covered with sand grains integratedly can strengthen output current, and to demonstrate zinc oxide nanowire of the present invention be homoepitaxial in large-area substrates.
The present invention measures the output voltage of above-mentioned model, the output voltage namely under the condition of number increasing nano generator in series connection integrated unit M.As shown in Fig. 5 (e), along with the number of nano generator increases from 1 to 3, namely press a
1, b
1and c
1order, their output voltage increases from 0.09,0.18 to 0.25V.Each unit due to integrated nano generator of connecting is subject to the impact of identical external force simultaneously, and their corresponding piezoelectricity electromotive forces under external pressure are cumulative, and therefore output voltage increases along with the number of nano generator in series connection integrated unit M.Equally, as shown in Fig. 5 (e), other series connection integrated unit a
2, b
2and c
2, a
3, b
3and c
3produce similar results, and these results clearly demonstrate, and series connection based on metal (preferred aluminium) substrate is integrated can strengthen output voltage.
Generally speaking, the nano generator based on the large-area metallic substrates being covered with sand grains is not only easy to parallel integrated to obtain not by the High Output Current of size restrictions, and is easy to integrated acquisition high output voltage of connecting.
As shown in Figure 6, in order to study the stability of nano generator of the present invention within the extended period, with series connection integrated unit M(c under the frequency of 2Hz
2part) their output voltage of continuous measurement 20 hours.After the running of 20 hours, series connection integrated unit M(c
2part) demonstrate good stability.In addition, as shown in Figure 7, connect integrated unit M(c
2part) output voltage be not obviously subject to affecting from the growth of the driving frequency of 2 to 8Hz.Because mankind's walking and moving vehicle occur usually under various low frequency, these stable results prove that nano generator of the present invention is hopeful to use in actual applications.
In addition, nano generator of the present invention can not only parallel series integrated to obtain by High Output Current and the voltage of size and restricted number, and can be applied to because robustness can be used in the surface of any geometry/shape, producing various mechanical energy on these surfaces by any one action or vibration.These advantages, except present solar cell, fuel cell, wind-driven generator and pyroelectric technology, also provide huge potentiality in results field of renewable energy.
Set forth the enforcement of method of the present invention below by specific embodiment, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
Embodiment
Experiment material used in embodiment is as follows:
| Material name | Producer and model |
| Diallyl dimethyl ammoniumchloride | Aldrich |
| Poly (sodium 4-styrenesulfonate) | Aldrich |
| Polymethyl methacrylate | Aldrich |
Embodiment 1
Select three pieces of purity 99.5% thickness 0.1mm, size 5 × 6cm
2industrial aluminium foil as substrate and electrode material.These three pieces of industrial aluminium foils are handled as follows respectively.
Be 4 kilograms/cm by the sand grains pressure of average grain diameter 50 μm
2blast injection on a face of aluminium foil, then use deionized water rinsing sandblasting aluminium foil.Adopt conventional injection sputter on the face of blasting treatment, generate the zinc oxide seed layer of a thickness 100nm at aluminium foil.
Adopt 0.1mol/L concentration by equimolar urotropine (HMTA) and zinc nitrate hexahydrate (ZnNO
3.6 (H
2o) nutrient solution) formed, the generation of aluminium foil there is facing down of zinc oxide seed layer, be placed on nutrient solution top, in mechanical convection heating furnace (model: YamatoDKN400 at 85 DEG C, California, Santa Clara) in growth 16 hours, the size of primary zinc oxide nanowire is approximately diameter 100-200nm, length about 2 μm.There is the aluminium foil of zinc oxide nanowire also dry in atmosphere with deionized water rinsing growth.
Aluminium foil is soaked 90 seconds respectively in diallyl dimethyl ammoniumchloride (PDADMAC) solution and poly (sodium 4-styrenesulfonate) (PSS), then dries.Polymethyl methacrylate (PMMA) layer of rotary coating thickness 2 μm on the face having zinc oxide nanowire is grown at aluminium foil
In three pieces of aluminium foils one piece is used as the bottom electrode (bottom) of nano generator, the face not having growth of zinc oxide nano line connects a wire.
Residue two pieces of aluminium foils are cut into size 1.1 × 1.4cm respectively
29 unit, be then stacked on bottom, stack two-layer altogether.Aluminium foil is split, obtains 9 pieces of size 1.1 × 1.4cm
2aluminium foil, as top electrodes, be connected with each top electrodes with 9 wires.Obtaining each series connection integrated unit M connects integrated by 3 nano generators, 9 parallel integrated integrated nanometer generator 1# of series connection integrated unit M.
Embodiment 2
The present embodiment method therefor is identical with embodiment 1, and difference is only to select purity 99.5% thickness 0.1mm, size 5 × 6cm
2industrial silver foil as substrate and electrode material.Sand grains average grain diameter 45 μm.Embodiment 2 obtains each series connection integrated unit M and connects integrated by 3 nano generators, 9 parallel integrated integrated nanometer generator 2# of series connection integrated unit M.
Embodiment 3
Select 20 pieces of purity 99.5% thickness 0.1mm, size 3.34 × 6cm
2industrial aluminium foil as substrate and electrode material.These two pieces of industrial aluminium foils are handled as follows respectively.
Be 4.5 kilograms/cm by the sand grains pressure of average grain diameter 70 μm
2blast injection on a face of aluminium foil, then use deionized water rinsing sandblasting aluminium foil.Adopt sputter on the face of blasting treatment, generate the zinc oxide seed layer of a thickness 100nm at aluminium foil.
Adopt 0.1mol/L concentration by equimolar urotropine (HMTA) and zinc nitrate hexahydrate (ZnNO
36 (H
2o) nutrient solution) formed, the generation of aluminium foil there is facing down of zinc oxide seed layer, be placed on nutrient solution top, in mechanical convection heating furnace (model: YamatoDKN400 at 85 DEG C, California, Santa Clara) in growth 16 hours, the size of primary zinc oxide nanowire is approximately diameter 100-200nm, length about 2 μm.There is the aluminium foil of zinc oxide nanowire also dry in atmosphere with deionized water rinsing growth.
Aluminium foil is soaked 90 seconds respectively in diallyl dimethyl ammoniumchloride (PDADMAC) solution and poly (sodium 4-styrenesulfonate) (PSS), then dries.Polymethyl methacrylate (PMMA) layer of rotary coating thickness 2 μm on the face having zinc oxide nanowire is grown at aluminium foil
In aluminium foil one piece is used as the bottom electrode (bottom) of nano generator, the face not having growth of zinc oxide nano line connects a wire.
All the other aluminium foils are cut into size 1.1 × 1.4cm
25 unit, be then stacked on bottom, stack 19 layers altogether.Aluminium foil is split, obtains 5 pieces of size 1.1 × 1.4cm
2aluminium foil, as top electrodes, be connected with each top electrodes with 5 wires.Obtaining each series connection integrated unit M connects integrated by 20 nano generators, 5 parallel integrated integrated nanometer generator 3# of series connection integrated unit M.
Embodiment 4
Select 10 pieces of purity 99.5% thickness 0.1mm, size 6.68 × 8cm
2industrial aluminium foil as substrate and electrode material.These 10 pieces of industrial aluminium foils carry out processing procedure substantially the same manner as Example 1, and difference is: sand grains average grain diameter 55 μm, and 9 pieces of aluminium foils are cut into size 1.1 × 1.4cm respectively
216 unit, be then stacked on bottom, stack 9 layers altogether.By size 1.1 × 1.4cm
2aluminium foil be used as top electrodes, be connected with each top electrodes with 16 wires.Obtaining each series connection integrated unit M connects integrated by 10 nano generators, 16 parallel integrated integrated nanometer generator 4# of series connection integrated unit M.
Embodiment 5
Select five pieces of purity 99.5% thickness 0.1mm, size 8.35 × 10cm
2industrial aluminium foil as substrate and electrode material.These five pieces of industrial aluminium foils carry out processing procedure substantially the same manner as Example 1, and difference is: sand grains average grain diameter 30 μm, and four pieces of aluminium foils are cut into size 1.1 × 1.4cm respectively
225 unit, be then stacked on bottom, stack four layers altogether.By size 1.1 × 1.4cm
2aluminium foil be used as top electrodes, be connected with each top electrodes with 25 wires.Obtaining each series connection integrated unit M connects integrated by 5 nano generators, 25 parallel integrated integrated nanometer generator 5# of series connection integrated unit M.
The output signal of nano generator is recorded with low noise voltage preamplifier (research on standard device, model SR560) and low noise electric current and voltage preamplifier (research on standard system model SR570).With sinusoidal servo controller (LabworksInc. company, model SC-121) and linear power amplifier (LabworksInc. company, model PA-119) put 1-5# nano generator with the frequency period of 2Hz according to defeating of 100N, output voltage and the output current value of 1-5# nano generator are as shown in table 1.
Table 1
Application Example
One of object of integrated nanometer generator of the present invention is from mankind's walking, to gather in the crops the strong nano generator of energy.In order to avoid the unexpected impact of undesirable electric noise may be caused between on-stream period, this device is fixedly secured on the smooth supporting plate that size is suitable.
Adopt the parallel series integrated nanometer generator of embodiment 1, the bottom electrode of this integrated nanometer generator adopts size 5 × 6cm
2industrial aluminium foil.Adopt size 29 × 13cm
2supporting plate this integrated nanometer generator is fixed.The Kapton Tape of the contact-making surface thickness about 15 μm of this nano generator and supporting plate insulate.
The people of 75kg, under single less touch with the ground 10cm, completes and once presses in 1s.As shown in Figure 8, the parallel series integrated nanometer generator of embodiment 1, shows maximum output voltage and the electric current of 3.2V and 595nA.
Although along with the change of the power acted on nano generator, the output current of nano generator is different with voltage, and under the walking style of different magnitude and frequency, nano generator of the present invention can produce corresponding power output.
Integrated nanometer generator of the present invention can from mankind's walking or other vibrations, harvest machinery energy moving vehicle, and this stored energy is applied to the such as electronic product such as mobile phone, reception of wireless signals transmitting.
Claims (25)
1. an integrated nanometer generator, has on the metal level of sand grains parallel integrated by least two series connection integrated unit M in large-area injection;
Described series connection integrated unit M is connecting integrated by least two nano generators perpendicular to metal level direction;
Described nano generator comprises: lower electrode layer, zinc oxide nano-wire array, polymeric dielectric layer and upper electrode layer, described zinc oxide nano-wire array vertical-growth is on lower electrode layer, described zinc oxide nano-wire array is coated with described polymeric dielectric layer, described zinc oxide nano-wire array covers by described polymeric dielectric layer, and described upper electrode layer is arranged on polymeric dielectric layer.
2. integrated nanometer generator according to claim 1, it is characterized in that, in described series connection integrated unit M, the bottom electrode at upper nano generator is used as at the top electrode of lower nano generator, described electrode is any one in gold, silver, platinum, aluminium, nickel, copper, titanium, chromium, tin or their alloy, and the surface of its growth of zinc oxide nano linear array is covered with sand grains.
3. integrated nanometer generator according to claim 2, is characterized in that, described electrode is aluminium.
4. the integrated nanometer generator according to any one of claim 1-3, is characterized in that, the average grain diameter of described sand grains is 30-70 μm.
5. integrated nanometer generator according to claim 4, is characterized in that, the average grain diameter of described sand grains is 45-55 μm.
6. the integrated nanometer generator according to claim 1-3,5 any one, is characterized in that, described series connection integrated unit M is 2 to 500, and in each series connection integrated unit M, nano generator is 2 to 500.
7. integrated nanometer generator according to claim 4, is characterized in that, described series connection integrated unit M is 2 to 500, and in each series connection integrated unit M, nano generator is 2 to 500.
8. integrated nanometer generator according to claim 6, is characterized in that, described series connection integrated unit M is 5 to 25, and in each series connection integrated unit M, nano generator is 3 to 20.
9. integrated nanometer generator according to claim 7, is characterized in that, described series connection integrated unit M is 5 to 25, and in each series connection integrated unit M, nano generator is 3 to 20.
10. according to claim 1-3,5, integrated nanometer generator described in any one of 7-9, it is characterized in that, described polymeric dielectric layer is polymethyl methacrylate or dimethyl silicone polymer.
11. integrated nanometer generators according to claim 4, is characterized in that, described polymeric dielectric layer is polymethyl methacrylate or dimethyl silicone polymer.
12. integrated nanometer generators according to claim 6, is characterized in that, described polymeric dielectric layer is polymethyl methacrylate or dimethyl silicone polymer.
13. according to claim 1-3,5, integrated nanometer generator described in any one of 7-9,11-12, it is characterized in that, described metal level is any one in gold, silver, platinum, aluminium, nickel, copper, titanium, chromium, tin or its alloy.
14. integrated nanometer generators according to claim 4, is characterized in that, described metal level is any one in gold, silver, platinum, aluminium, nickel, copper, titanium, chromium, tin or its alloy.
15. integrated nanometer generators according to claim 6, is characterized in that, described metal level is any one in gold, silver, platinum, aluminium, nickel, copper, titanium, chromium, tin or its alloy.
16. integrated nanometer generators according to claim 10, is characterized in that, described metal level is any one in gold, silver, platinum, aluminium, nickel, copper, titanium, chromium, tin or its alloy.
17. integrated nanometer generators according to claim 13, it is characterized in that, described metal level is aluminium.
18. integrated nanometer generators according to any one of claim 14-16, it is characterized in that, described metal level is aluminium.
The preparation method of 19. 1 kinds of integrated nanometer generators as described in any one of claim 1-18, the method comprises the steps:
A. sand grains is ejected on a surface of metal level, obtains the metal level that one face is covered with sand grains;
B. in the metal level being covered with sand grains, form Seed Layer, vertical-growth zinc oxide nano-wire array in the Seed Layer of metal level, then, by spin-coating method, polymeric dielectric layer is covered on zinc oxide nano-wire array layer;
C. at least step a and b is repeated once;
D. using one of them in gained metal level as bottom electrode, all the other metal levels be used as outside bottom electrode are divided at least two unit respectively, then described unit are stacked on bottom electrode, form at least double-layer structure body;
E. on each nano generator of top layer, place top electrode metal layer respectively, obtain integrated nanometer generator.
The preparation method of 20. integrated nanometer generators according to claim 19, is characterized in that, in step a, is 3.5-4.5 kilogram/cm by the sand grains pressure of average grain diameter 30-70 μm
2blast injection to aluminium lamination surface.
The preparation method of 21. integrated nanometer generators according to claim 20, is characterized in that, in step a, is 4 kilograms/cm by the sand grains pressure of average grain diameter 45-55 μm
2blast injection to aluminium lamination surface.
The preparation method of 22. integrated nanometer generators according to claim 19, it is characterized in that, in stepb, on the seed layer after growth of zinc oxide nano linear array, metal level is soaked 70-120 second respectively in diallyl dimethyl ammoniumchloride and poly (sodium 4-styrenesulfonate).
The preparation method of 23. integrated nanometer generators according to claim 20 or 21, it is characterized in that, in stepb, on the seed layer after growth of zinc oxide nano linear array, metal level is soaked 70-120 second respectively in diallyl dimethyl ammoniumchloride and poly (sodium 4-styrenesulfonate).
The preparation method of 24. integrated nanometer generators according to claim 22, it is characterized in that, in stepb, on the seed layer after growth of zinc oxide nano linear array, metal level is soaked 90 seconds respectively in diallyl dimethyl ammoniumchloride and poly (sodium 4-styrenesulfonate).
The preparation method of 25. integrated nanometer generators according to claim 23, it is characterized in that, in stepb, on the seed layer after growth of zinc oxide nano linear array, metal level is soaked 90 seconds respectively in diallyl dimethyl ammoniumchloride and poly (sodium 4-styrenesulfonate).
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