CN104734565B - A kind of generator and electricity-generating method for collecting working fluid energy - Google Patents
A kind of generator and electricity-generating method for collecting working fluid energy Download PDFInfo
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- CN104734565B CN104734565B CN201310714104.4A CN201310714104A CN104734565B CN 104734565 B CN104734565 B CN 104734565B CN 201310714104 A CN201310714104 A CN 201310714104A CN 104734565 B CN104734565 B CN 104734565B
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Abstract
It the invention provides a kind of generator and electricity-generating method, can be used to collect the energy of flow of liquid, working fluid energy particularly present in environment, and convert it into electric power and directly use or storage.If generator main easily rubbed using such as water of liquid in environment with other materials after powered characteristic and electrostatic conduction principle, can widely collect such as the mechanical energy that waste water flows in rain raindrop and environment, and be transformed into electric energy, have broad application prospects.
Description
Technical field
The present invention relates to electrostatic generating technical field, more particularly to a kind of energy by various working fluids in environment converts
For the generator and electricity-generating method of electric energy.
Background technology
Various kinetic energy and potential energy can be constantly produced during nature and human life's survival, how by these small energy
Amount is changed into driving force source needed for us, is people in the direction constantly sought.The it is proposed of nano generator in 2006, is opened
Ward off a new field of existing small energy conversion and application everywhere in environment.On this basis, the friction of proposition
Generator passes through special device structure design so that this ancient phenomenon of triboelectrification shows new application value and dived
Power.Whole friction electric generator is then by the charge pump effect of friction potential, the polymer film for being coated with metal electrode by two kinds
Fit together composition device, and device produces mechanical deformation under external force, causes to occur mutually between two layers of polymers film
Friction, so as to produce separation of charge and form electrical potential difference.Electric energy output end of two metal polar plates as generator, passes through electrostatic
Sensing can be in Surface Creation charge inducing, and charge inducing flows through external circuit under friction potential driving can form electric current.
However, the design of friction generator is only limitted to the utilization of the frictional energy between solid and solid at present, it is impossible to using in environment
The mechanical energy that contains of liquid motion.
The content of the invention
The invention provides a kind of generator simple in construction, can be electric energy by the energy conversion of working fluid.
The generator provided by the invention for collecting working fluid energy, including：Conducting element；Frictional layer, the frictional layer
Lower surface cover all conducting element；When electrically charged drop or the upper surface of the liquid of flowing and the frictional layer
Separate afterwards, the conducting element can produce charge inducing and outwards export electric signal.
Preferably, liquid of the electric charge of the drop or the liquid of flowing institute band from the drop or flowing and other materials
The friction of material.
Preferably, the upper surface of the frictional layer is for electroneutral or with electric charge.
Preferably, the material of the frictional layer is insulating materials.
Preferably, the insulating materials selects following one or more：Aniline-formaldehyde resin, polyformaldehyde, ethyl cellulose,
Polyamide nylon 11, polyamide nylon 66, wool and its fabric, silk and its fabric, paper, polyethylene glycol succinate, fiber
Element, cellulose acetate, polyethyleneglycol adipate, polydiallyl phthalate, regenerated cellulosic sponge, cotton and its knit
Thing, polyurethane elastomer, SAN, SB, wood, hard rubber, acetate, people
Make fiber, polymethyl methacrylate, polyvinyl alcohol, polyester, polyisobutene, elastic polyurethane sponge, poly terephthalic acid second
Diol ester, polyvinyl butyral resin, hycar, neoprene, natural rubber, polyacrylonitrile, poly- (inclined chlorine
Ethylene-co-propylene nitrile), it is poly bisphenol carbonic ester, CPPG, polyvinylidene chloride, poly-（2,6- dimethyl polyphenylene aoxidizes
Thing）, polystyrene, polyethylene, polypropylene, poly- diphenyl propane carbonic ester, polyethylene terephthalate, polyimides,
Polyvinyl chloride, dimethyl silicone polymer, polytrifluorochloroethylene, polytetrafluoroethylene (PTFE) and Parylene.
Preferably, the material of the frictional layer is semiconductor, and the semiconductor selects following one or more of materials：Silicon,
The compounds of group of the compounds of group of germanium, the IIIth and the Vth, the IIth and the VIth, and by III-V compounds of group and II-VI compounds of group group
Into solid solution；Or the material of the frictional layer be selected from manganese, chromium, iron, the oxide of copper, or silica, zinc oxide,
BiO2And Y2O3。
Preferably, the part or all of upper surface of the frictional layer includes micro-nano structure layer, and the micro-nano structure layer choosing is certainly
Nano wire, nanotube, nano particle, nanometer rods, nano flower, nanometer channel, micron trenches, nanocone, micron cone, nanosphere and
Micron chondritic, and the array formed by aforementioned structure.
Preferably, directly formed when the micro-nano structure layer is and prepares the frictional layer；Or the micro-nano structure layer is
Interspersed in the upper surface of frictional layer or coated with nano material layer is formed；Or the micro-nano structure layer is by photoengraving, changed
The methods of learning etching and plasma etching prepares in the upper surface of frictional layer.
Preferably, either micro-nano structure layer is hydrophilic or hydrophobic structure to the frictional layer.
Preferably, the upper surface of the frictional layer is hydrophobic material, and the liquid is polar liquid；Or the friction
The upper surface of layer is water wetted material, and the liquid is nonpolar liquid.
Preferably, polar liquid is water, formic acid, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, acetic acid, dimethyl Asia
Sulfone, dimethylformamide, acetonitrile or acetone；The nonpolar liquid be hexane, benzene, toluene, diethyl ether, chlorine walk back and forth, ethyl acetate,
Tetrahydrofuran or dichloromethane.
Preferably, the upper surface of the frictional layer or the liquid pass through chemical modification.
Preferably, the chemical modification makes in the frictional layer upper surface and the liquid, in polarity is positive material
Introduce the functional group for being more easy to betatopic（I.e. strong electron donating group）, or, introduce the electronics that is more easy to get in polarity is negative material
Functional group（Strong electron-withdrawing group group）；Or the chemical modification makes the frictional layer with being positive in polarity in the liquid
Positive charge is introduced in material；Or introduce negative electrical charge in polarity is negative material.
Preferably, the strong electron donating group includes：Amino, hydroxyl or alkoxy；The strong electron-withdrawing group group includes：Acyl
Base, carboxyl, nitro or sulfonic group.
Preferably, the micro-nano structure layer of the frictional layer upper surface is identical with the material of the frictional layer.
Preferably, the frictional layer is hard material or flexible material.
Preferably, its thickness range of the frictional layer is 50nm~2cm.
Preferably, the thickness of the micro-nano structure layer is between 20nm~20 μm.
Preferably, in addition to：Substrate, the conducting element are arranged on the substrate top surface；The frictional layer with it is described
The conducting element is completely covered substrate.
Preferably, in addition to：Substrate, the substrate upper and lower surface set a conducting element respectively；Described in two
The frictional layer is covered on conducting element.
Preferably, the material of the substrate is hard material or flexible material.
Preferably, the material choosing of the conducting element uses metal, conductive oxide or conducting polymer.
Preferably, the conducting element is to deposit the film to be formed in the lower surface of the frictional layer.
Preferably, the conducting element is hard material or flexible material, and its thickness is between 10nm~500 μm.
Preferably, the conducting element electrically connects with ground potential or equipotential source.
Preferably, the frictional layer, conducting element and substrate are transparent material.
Accordingly, the present invention also provides a kind of electricity-generating method using engine described in any of the above-described, electrically charged liquid
Drop or the liquid of flowing produce charge inducing in conducting element and outwards exported with being separated after the upper surface of the frictional layer
Electric signal.
Preferably, the upper surface of the drop or the liquid of flowing after being charged by friction with the frictional layer.
Preferably, the distance that the drop or fluid friction are passed through is in more than 20cm.
The generator that working fluid energy can be collected and electricity-generating method provided by the invention have the advantages that：
The generator for collecting working fluid mechanical energy is proposed first, mainly utilizes the phenomenon to be rubbed in nature
And the principle of electrostatic conduction, using easy structure design, realize and collect liquid in the environment（Particularly water）Mobile handling machinery
The possibility of energy；And the electric signal output that generator of the present invention is provided can be used directly or store；
（2）In generator, micro-nano structure layer is formed directly into frictional layer upper surface, being capable of the significant electricity for improving generator
Signal output performance, broken needs first to prepare the limitation that frictional layer forms nanostructured in friction layer surface again in the past, significantly
Simplify preparation method, reduce cost, while also provide a new approach for the optimization output of electric signal；
（3）In the upper surface of frictional layer, design micro-nano structure layer has two important meanings, and one is the ripple that can coordinate liquid
The contact area of dynamic increase frictional layer and liquid surface, if another is the mechanical energy for wanting to collect the larger liquid of polarity, such as water, this
Structure can increase the hydrophobicity of frictional layer, make water can be completely separable after being contacted with frictional layer, there is provided larger electricity output；
（4）The micro-nano structure layer of tool hydrophobicity or super-hydrophobicity has self-cleaning function simultaneously, will be helpful to generator
Frictional layer maintains a clean surface, especially for using in large natural environment out of doors, it is ensured that can provide for a long time effectively defeated
Go out.
（5）The contact generator based on liquid of the present invention, the size of its critical piece can coordinate the face of environment reclaimed water
Product and volume carry out size adjusting, and can be prepared into flexible or solid structure, can be widely applied for various fields.And generate electricity
The structure of machine is simple, and all material prices are cheap and are readily available, and therefore, generator of the invention is easy to make, cost
It is low, it is easy to industry promotion and application.
Brief description of the drawings
By the way that shown in accompanying drawing, above and other purpose of the invention, feature and advantage will become apparent from.In whole accompanying drawings
Identical reference instruction identical part.Deliberately accompanying drawing is not drawn by actual size equal proportion scaling, it is preferred that emphasis is show
Go out the purport of the present invention.
Fig. 1 is the structural representation for the generator for collecting working fluid energy；
Fig. 2 is that generator collects the operation principle schematic diagram singly dripped；
Fig. 3 is the operation principle schematic diagram that generator collects continuous water droplet or circulating water；
Fig. 4 is the structural representation for possessing double-deck generator according to the present invention；
Fig. 5 be for repeatedly collect water droplet energy combined generator system, wherein comprising the present invention generator and
The generator of traditional bipolar electrode structure；
Fig. 6 is that a specific generator collects the output voltage singly to drip, electric current, measured sense is fallen with different distance
Answer output voltage, electric current, power and the energy under the quantity of electric charge, and the different resistance of connection；
Fig. 7 is the output current density that generator is applied to collect tap outflow water energy, and rectified straight
The bright 20 LEDs bulb of contact and the voltage pattern of the electric capacity charging for 33 μ F；
Fig. 8 is the output current density for utilizing the continuous water droplet of combined generator systematic collection, and rectified direct point
Bright 20 LEDs bulb and the voltage pattern of the electric capacity charging for 33 μ F.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in more detail.It should be noted that in accompanying drawing or specification description, similar or identical portion
Divide and all use identical figure number.In addition, though the demonstration of the parameter comprising particular value can be provided herein, but parameter is without definite etc.
In corresponding value, but can be similar to be worth accordingly in acceptable error margin or design constraint.In addition, following examples
In the direction term mentioned, such as " on ", " under ", "front", "rear", "left", "right" etc., be only refer to the attached drawing direction.Therefore,
The direction term used is intended to be illustrative and not intended to limit the present invention.
The generator of collection working fluid energy in the present invention, is easily rubbed using liquid in environment with other materials
And make that itself is powered, or generator use frictional layer also easy to be powered in itself, and can electrically maintain long-time to exist, using water as
Example, when water drippage or circulating water contact frictional layer leave again, can make in generator conducting element generation charge inducing, and then
Cause the transfer of external circuit electronics, that is, the output of generator.This electricity-generating method, which can be used in, collects flow fluid in environment
The energy of body, such as rainy raindrop, family and industrial wastewater, waterfall, even wave, tide.
The typical structure of the generator of the present invention includes referring to Fig. 1, generator：Substrate 12, the upper surface of substrate 12 are set
Have covered with frictional layer 10 on conducting element 11, and conducting element 11, frictional layer 10 must be bonded completely with substrate 12, by conduction
The all coverings of element 11；The wire for being connected to conducting element is additionally included, for exporting electric signal, is not shown in Fig. 1.
The generator of the present invention, it is different corresponding to the motor pattern of liquid in natural environment, and can have two kinds
Mode of operation.By taking liquid water as an example, a kind of is no matter the upper surface band of frictional layer 10 is not charged, when powered water droplet is fallen, and energy
It is enough contacted with the upper surface of frictional layer 10 at least part after separate, can be to produce electric signal output in conducting element 11；In addition
A kind of pattern is, when water droplet is fallen and very high density to be continuous, or during the water continuously to flow, now in the upper of frictional layer 10
Surface easily remains thin water layer, now when being separated after water powered in addition falls and contacted with this thin water layer again, can equally lead
Electric device 11 produces electric signal output.Certainly, we are very difficult to distinguish generator is which kind of Working mould belonged on earth in the environment
Formula, because may be simultaneously present both mode of operations.No matter which kind of pattern, as long as water can be with the upper surface of frictional layer when falling
Back and forth switch between contact condition and released state, you can form charge inducing in conducting element, exchange is produced to external circuit
Pulse electrical signal exports.
In order to improve the output performance of generator, preferably include in all or part of upper surface of frictional layer 10 nanometer,
The micro-nano structure layer of micron or secondary micron dimension, when water is fallen or frictional layer 10 makes the upper surface of frictional layer 10 be connect with water close to water
When touching, the setting of micro-nano structure layer can increase effective contact area of the upper surface of frictional layer 10 and water, improve charge inducing
Density.The effect of the micro-nano structure layer of frictional layer upper surface is except further increasing the contact surface between frictional layer upper surface and water
Product is outer, can also play the hydrophobicity of regulation frictional layer 10, control frictional layer contacted every time with water after separation degree.Therefore,
Preferably, the micro-nano structure layer of frictional layer upper surface is super-hydrophobic nano material, such as zinc oxide, polytetrafluoroethylene (PTFE), poly- diformazan
The nanowire array structures such as radical siloxane, particularly the lotus leaf surface either super-hydrophobic nano structure layer such as insect foot.
Furthermore it is possible to according to the hydrophilic or hydrophobic performance of the upper surface of frictional layer 10, the polarity of liquid is selected, to increase liquid
Charge inducing density when body separates with frictional layer upper surface.Preferably, the top surface of frictional layer 10 is hydrophobic material
Material, the liquid is polar liquid；Or the upper surface of frictional layer 10 is water wetted material, liquid is nonpolar liquid.Polar liquid
Body can be water, formic acid, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, acetic acid, dimethyl sulfoxide (DMSO), dimethylformamide,
Acetonitrile or acetone etc., nonpolar liquid can be hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran or dichloro
Methane.
Micro-nano structure layer is preferably nano wire, nanotube, nano particle, nanometer rods, nano flower, nanometer channel, micron ditch
Groove, nanocone, micron cone, nanosphere and micron chondritic, and the array formed by aforementioned structure, particularly by nanometer
The nano-array of line, nanotube or nanometer rods composition.The size of each this unit is in nanometer to micron dimension in array, specifically
Unit size, shape in micro nano structure layer should not limit the scope of this invention.The micro-nano structure of the upper surface of frictional layer 10
Layer can be by being prepared the methods of photoengraving, chemical etching and plasma etching in the lower surface of frictional layer, or
Preparing friction layer material makes directly to be formed.Preferably, the thickness of micro-nano structure layer is between 20nm~20 μm.
In addition, in order to achieve the above object, it can also be interspersed in the upper surface of frictional layer or coated with nano material is formed
State micro-nano structure layer.The nano material can be selected from nano particle, nanotube, nano wire and nanometer rods.Can according to being actually needed
To be chosen in particular from nano SiO 2 particle, nanometer silica line, silicon dioxide nano rod, Silica Nanotube, poly- two
Methylsiloxane nano particle, dimethyl silicone polymer nano wire or dimethyl silicone polymer nanometer rods, dimethyl silicone polymer
Nanotube, polytetrafluorethylenano nano particle, polytetrafluorethylenano nano line, polytetrafluorethylenano nano rod and polytetrafluorethylenano nano
Pipe.Below with reference to accompanying drawing, each part of the generator of the collection working fluid energy to the present invention is carried out specifically
It is bright.
The generator of the present invention, the motion of either liquid make the upper surface of frictional layer in contact condition and be separated with liquid
Back and forth switch between state, or make frictional layer with liquid in contact condition and released state by controlling the movement of frictional layer
Between back and forth switch, between conducting element formed alternating-current pulse output process be similar, frictional layer is made with the motion of water
Upper surface and water between contact condition and released state exemplified by reciprocal switching, with reference to Fig. 1 electric generator structure, to single water
The course of work of drop is specifically described, referring to Fig. 2：
(1) referring to Fig. 2（a）, powered water droplet falls by certain altitude, not yet touches the upper surface of frictional layer 10（Bag
Include micro-nano structure layer）, now conducting element 11 there is no charge inducing, generator is also without output；
(2) referring to Fig. 2（b）, powered water droplet is partially exposed to the upper surface of frictional layer 10（Including micro-nano structure layer）, by
In electrostatic interaction, cause electronics to flow to conducting element 11 from big ground terminal, now just produce the output of forward direction；
(3) referring to Fig. 2（c）, powered water droplet more parts touch the upper surface of frictional layer 10（Including micro-nano structure
Layer）, more electronics flow to conducting element 11 from big ground terminal, finally up to balance；
(4) referring to Fig. 2（d）, when powered water droplet is from the upper surface of frictional layer 10（Including micro-nano structure layer）Leave, make
Big ground terminal is flowed to from conducting element 11 again into electronics, reverse output is now produced, eventually passes back to reset condition, referring to Fig. 4.
It can be seen that when the reciprocal switching between contact condition and released state of the upper surface of frictional layer 10 and water, it is caused on
State alternating-current pulse electric signal to be exported by the lead-out wire of conducting element, so as to form pulse signal.
The example of water droplet or circulating water for continuation can be found in Fig. 3：
(1) referring to Fig. 3（a）, powered water droplet falls by certain altitude, not yet touches the upper surface of frictional layer 10（Bag
Include micro-nano structure layer）, now conducting element 11 there is no charge inducing, generator is also without output；
(2) referring to Fig. 3（b）, because the frequency that water is fallen is too fast, the water droplet contacted first with frictional layer 10 is easily in frictional layer
10 upper surface（Including micro-nano structure layer）A very thin powered water layer is formed, and the sense of equivalent is produced on conducting element 11
Answer electric charge, generator is without output during balance；
(3) referring to Fig. 3（c）, follow-up powered water drop contact, due to electrostatic interaction, causes electronics to the upper surface of water layer
Conducting element 11 is flowed to from big ground terminal, now just produces the output of forward direction；
(4) referring to Fig. 3（d）, with the increase of powered water droplet and frictional layer contact area, more electronics are from big ground terminal stream
Conductive member 11, finally up to balance, generator is also without output；
(5) referring to Fig. 3（e）, when powered water droplet leaves from the upper surface of water layer, cause electronics again from conducting element 11
Big ground terminal is flowed to, reverse output is now produced, eventually passes back to reset condition, referring to Fig. 3（b）.
It can be seen that when the reciprocal switching between contact condition and released state of water and water layer upper surface, caused above-mentioned friendship
Stream pulse electrical signal is exported by the lead-out wire of conducting element, so as to form pulse signal.
In practice, the upper surface of frictional layer 10 is by the effect such as friction of other objects, and its usual upper surface is with a small amount of
Electric charge, and the electric charge can retain for a long time.In the case of the upper surface of the frictional layer 10 of generator carries electric charge, it is sent out
Electric principle is similar with Fig. 3, no longer repeats herein.
In the generator of the present invention, the requirement introduction to the hardness of frictional layer 10, thickness, shape and material etc.
It is as follows：
（1）The present invention micro-nano structure layer that restriction frictional layer 10 or frictional layer upper surface include must be hard material
Material, can also select flexible material, because the hardness of material has no effect on the contact effect of frictional layer 10 with water therebetween, this
The technical staff in field can be selected according to actual conditions.
（2）The thickness of frictional layer 10 has significant impact to the performance of the generator of the present invention, simply during preparation
Need to consider the factor such as frictional layer intensity and hydrophobic effect and generating efficiency.Preferably frictional layer of the invention is thin layer, thickness
For 50nm~2cm, preferably 100nm~1cm, more preferably 500nm~5mm, more preferably 1 μm~2mm, these thickness are in the present invention
All technical schemes are all suitable for.The thickness of frictional layer 10 gets over Bao Yuehao, but because prior art is limited to, most preferably 1 μm~
100μm。
（3）The present invention is not particularly limited to the shape of frictional layer 10 and the micro-nano structure layer of frictional layer upper surface, only
Ensure that the upper surface of frictional layer 10 at least partly contacts with liquid.But in order to obtain more preferable pulse signal
Output performance, the performance of frictional layer upper surface are preferably engaged with the property of liquid, if liquid is the big liquid water of polarity, are rubbed
The composition and structure for wiping layer upper surface are preferably water transport structure and super water transport structure, just can ensure that energy after frictional layer 10 and water contact
Separate as far as possible, to produce maximum charge inducing density.
In the friction generator of the present invention, the micro-nano structure layer of frictional layer upper surface can be with the material phase of frictional layer 10
Together, can also be different, it is preferably identical.The material of frictional layer 10 or the micro-nano structure layer of frictional layer upper surface can be insulation
Material.Some conventional insulating materials are enumerated herein：Aniline-formaldehyde resin, polyformaldehyde, ethyl cellulose, polyamide nylon 11,
Polyamide nylon 66, wool and its fabric, silk and its fabric, paper, polyethylene glycol succinate, cellulose, cellulose acetate
Ester, polyethyleneglycol adipate, polydiallyl phthalate, regenerated cellulosic sponge, cotton and its fabric, elastic polyurethane
Body, SAN, SB, wood, hard rubber, acetate, staple fibre, poly- methyl
Methyl acrylate, polyvinyl alcohol, polyester, polyisobutene, elastic polyurethane sponge, polyethylene terephthalate, polyethylene
Butyral, hycar, neoprene, natural rubber, polyacrylonitrile, poly- (vinylidene chloride-co- propylene
Nitrile), it is poly bisphenol carbonic ester, CPPG, polyvinylidene chloride, poly-（2,6- dimethyl polyphenylene oxides）, polystyrene,
Polyethylene, polypropylene, poly- diphenyl propane carbonic ester, polyethylene terephthalate, polyimides, polyvinyl chloride, poly- two
Methylsiloxane, polytrifluorochloroethylene, polytetrafluoroethylene (PTFE) and Parylene.Parylene, including Parylene C, Parylene N, Parylene
D, Parylene HT and Parylene AF4.
Semiconductor can also replace insulator as the micro-nano structure layer for preparing frictional layer 10 or frictional layer upper surface
Raw material.Conventional semiconductor includes：Silicon, germanium；IIIth and the Vth compounds of group, such as GaAs, gallium phosphide etc.；IIth and the VIth
Compounds of group, such as cadmium sulfide, zinc sulphide etc.；And the solid solution being made up of III-V compounds of group and II-VI compounds of group,
Such as gallium aluminum arsenide, gallium arsenic phosphide etc..In addition to above-mentioned Crystalline Semiconductors, also amorphous glass semiconductor, organic semiconductor etc..It is non-
Electroconductive oxide, conductor oxidate and complex oxide also have triboelectric characteristics, can form surface in friction process
Electric charge, therefore the frictional layer as the present invention is may also be used for, such as the oxide of manganese, chromium, iron, copper, in addition to silica, oxygen
Change manganese, chromium oxide, iron oxide, cupric oxide, zinc oxide, BiO2And Y2O3。
As space is limited the reason for, can not be to all possible as frictional layer or the micro-nano structure of frictional layer upper surface
The material of layer carries out exhaustion, only lists several specific materials herein and is referred to for people, but it is clear that these specific materials are simultaneously
The restrictive factor of the scope of the present invention can not be turned into, because under the enlightenment of invention, those skilled in the art is according to rubbing
Triboelectric characteristics possessed by wiping layer material and liquid are easy to the material for selecting other similar.
Preferably, the material of micro-nano structure layer and the material of frictional layer are identical, using the polytetrafluoroethylene (PTFE) of hydrophobic composition, gather
Dimethyl siloxane, polyethylene（PE）, polypropylene（PP）, polystyrene（PS）, polymethyl methacrylate（PMMA）Or poly- pair
Polyethylene terephthalate（PET）.
Existing method for preparing template can be used, directly in frictional layer material upper surface while preparing friction layer material
Micro-nano structure layer is formed, with first preparing friction layer material, then wiener structure sheaf is prepared in the upper surface of frictional layer and compares, this hair
The method of bright middle use simplifies preparation method, reduces cost, while is also provided for the electric signal optimization output of generator
One new approach.
In addition it is also possible to carry out chemical modification to the upper surface of frictional layer 10 or liquid, contact wink can be further improved
Between the carried charge of liquid or frictional layer, so as to improve the power output of charge inducing density and generator.Chemical modification is divided into again
The following two kinds type：
A kind of method is to compare the polarity of frictional layer and two kinds of materials of liquid, introduces and is more easy in polarity is positive material
The functional group of betatopic（I.e. strong electron donating group）；Or the functional group for the electronics that is more easy to get is introduced in polarity is negative material
（Strong electron-withdrawing group group）.This method can further improve the carried charge of liquid and frictional layer Contact liquid, so as to carry
The power output of high charge inducing density and generator.Strong electron donating group includes：Amino, hydroxyl, alkoxy etc.；Strong electrophilic
Group includes：Acyl group, carboxyl, nitro, sulfonic group etc..Preferably, the introducing of functional group is carried out in the upper surface of frictional layer；Function
The introducing of group can be with conventional methods such as using plasma surface modifications.Such as the gaseous mixture of oxygen and nitrogen can be made certain
Plasma is produced under power, so as to introduce amino in frictional layer material upper surface.
Another method is to compare the polarity of frictional layer and two kinds of materials of liquid, is introduced in polarity is positive material
Positive charge；Or introduce negative electrical charge in polarity is negative material.The step of introducing electric charge can specifically pass through chemical bonding
Mode is realized.For example, positive silicic acid can be modified using the method for sol-gel on the surface of dimethyl silicone polymer frictional layer
Ethyl ester, and make its negatively charged.Those skilled in the art can according to the electrical of prevailing circumstances liquid or the easy band of frictional layer and
The species of surface chemistry key, selection is suitable material modified bonded thereto, to reach the purpose of the present invention, therefore can realize
State purpose chemical modification material and method all within protection scope of the present invention.Because the generator of the present invention can be applied
The energy of working fluid such as rainwater in nature is collected, it is preferred that introduce electric charge in the upper surface of frictional layer.
（4）The present invention does not have particular/special requirement to the spacing of the upper surface of frictional layer 10 and liquid, but in order that is transported in liquid
During dynamic, via windage process, the surface energy of liquid is set to produce larger charging property, the preferably spacing should be greater than 20cm
More than.Certainly, liquid obtains surface charge by rubbing, except with addition to windage, can also be with the liquid flow pathway such as water pipe
Other materials friction on footpath obtains surface charge.
Conducting element 11 is capable of conductive characteristic as the electrode of generator, it is necessary to possess, and can select conventional conduction
Material, the selection of the specific material of conducting element 11 is not as the factor for limiting the scope of the present invention, material commonly used in the art
For：Metal, selected from gold, silver, platinum, aluminium, nickel, copper, titanium, chromium or selenium；By gold, silver, platinum, aluminium, nickel, copper, titanium, chromium and selenium, Yi Jiyou
The alloy that above-mentioned metal is formed；Conductive oxide, such as tin indium oxide ITO；Organic matter conductor is generally conducting polymer, can be with
Select from polypyrrole, polyphenylene sulfide, poly- phthalocyanine-like compound, polyaniline and/or polythiophene.Preferably, the material of conducting element 11
Expect for copper, gold, silver or platinum.The larger conductive material of thickness can also be directly fitted on backing material to fix conductive element
Part.
In the friction generator of the present invention, conducting element 11 is preferably in close contact with the lower surface of frictional layer 10, to ensure
The induced efficiency of electric charge；The method of deposition can be used to prepare conducting element 11, such as electron beam in the lower surface of frictional layer 10
The methods of evaporation, plasma sputtering, magnetron sputtering or evaporation.Further, it is also possible to directly it is used as conducting element by the use of metallic plate
11, it is electrically connected with frictional layer with conducting resinl.
Conducting element 11 can also can provide the equipotential source electricity of electric charge in addition to it can be connected with ground potential with other
Connection, when the electric field of conducting element annex changes, equipotential source can provide enough electric charges to balance the electric field
Change.During generator operation, electric charge flowing is produced between conducting element 11 and ground potential or equipotential source, can be in conduction
Load, the output for electric signal are connected between element and ground potential or equipotential source.
Conducting element 11 can be film or thin layer, and the optional scope of thickness is 10nm~2cm, preferably 50nm~5mm,
More preferably 100nm~1mm, more preferably 500nm~500 μm, more preferably 1 μm~100 μm.Conducting element must not necessarily limit
Surely it is hard or flexible, because flexible conductive element can equally play support to frictional layer and conductive make
With.Conducting element is connected to export the electric signal of friction generator by wire or thin metal layer with external circuit.
In previous embodiment, generator includes substrate 12, in other embodiments, as long as the intensity foot of conducting element 11
It is enough, substrate 12 can also be omitted.Because the generator application of the present invention is in liquid, therefore, as long as the lower surface energy of frictional layer
Conducting element is enough covered, ensures that liquid will not directly contact with the conducting element of generator.It is therefore possible to use frictional layer
Directly conducting element is completely covered for material.
Another feature of the present invention is that substrate 12, conducting element 11 and frictional layer 10 can be soft or rigid substrate, and
According to the selection of substrate, the size and thickness of whole generator are handling greatly, this for there is great benefit in practical application,
Such as the collection of waterfall and wave energy, we can prepare large-sized generator.In the part of rainwater, except big face
Product, preferably conducting element, substrate and frictional layer are transparent material so that whole generator is high light transmittance, is adapted for use with glass
On glass.Other family and the collection of industrial wastewater energy, then can prepare laminar generator, can once insert it is multiple in
Specific water can flow the place of process, with up to the purpose effectively utilized.Technical staff can be according to the actual use feelings of generator
Condition makes suitable selection, should not limit the scope of the invention herein.
The generator of the present invention can be used for collecting the energy of flow of various liquid, as long as liquid can be with itself with electricity
Lotus, you can electric energy output is produced during being separate with generator.Typical liquid can be water, particularly rainwater, sea
Water, running water etc..Other liquid, such as toluene, dimethylbenzene, hexamethylene, petroleum ether, Mineral spirits, Vinylidene Chloride, ether or tetrachloro
Change carbon etc..
Referring to Fig. 4, generator of the invention can make full use of substrate to prepare the generator of bilayer, in the upper following table of substrate
Face respectively sets a generator, i.e., respectively sets a conducting element 11 in the upper and lower surface of substrate, and in each conducting element
Upper covering frictional layer 10, the frictional layer can be that entirety can also be two discrete friction Rotating fields, make conducting element complete
Covered by substrate and frictional layer, the energy of the working fluid of substrate both sides can be collected respectively, for collecting flow fluid in environment
The mechanical energy of body will more efficiently.
Referring to Fig. 5, the collection for rainwater energy can be again with the bipolar electrode structure generator for closing a traditional working mode
13 form a combined generator system, after the generator of raindrop and the present invention is separate（Process I）, fall in traditional work
The generator 12 of operation mode（Process II）Come up the mechanical energy of secondary collection rainwater, to reach more effectively using rainwater energy
Purpose.
Illustrate the performance of the friction generator of the present invention with a specific example below.It is poly (methyl methacrylate) plate with substrate 12
Material, frictional layer 10 are polytetrafluoroethylene (PTFE), the micro-nano structure layer of frictional layer upper surface is column polytetrafluorethylenano nano works,
Conducting element 11 is Copper thin film, and 30 microlitres of water droplet is fixed as using motoring syringe generation volume, is fallen and frictional layer upper table
Face produces contact and the cyclically-varying separated, wherein, the size of generator is 5cm × 5cm, when water droplet height of fall is 90cm
When, speed is about 1 meter per second, by Fig. 6（a）Figure with（b）From the point of view of figure, the output voltage that now generator can be provided is 9.5V,
Output current is 16 μ A, it can be seen that frictional layer and water are in the case where being contacting and separating, repeated splendid, the expression generating of output
The stability of machine is fine.
In Fig. 6（c）Figure, which is water droplet, falls charge inducing amount on measured conducting element from different height, it can be seen that water
Drop height of fall reaches more than 20cm, and its charge inducing amount almost reaches saturation value.
In Fig. 6（d）Figure is that water droplet is highly fallen from 90cm, measured output voltage and output in the case where connecting different resistance
Current value, output voltage are about 9.5V, and current value is about 10 μ A.
In Fig. 6（e）Figure is that water droplet is highly fallen from 90cm, and in the case where connecting different resistance, measured power output, can see
It is 110 μ W to go out the maximum when connecting resistance and being 5M Ω.
In Fig. 6（f）Figure is that water droplet is highly fallen from 90cm, and in the case where connecting different resistance, measured output energy, can see
It is 40nJ to go out the maximum when connecting resistance and being 5M Ω.
Fig. 7 is used for actual recycled water in family tap of collecting by generator of the present invention and reserves current（Falling water in figure
At stream arrow instructions）Energy.（a）Figure is the current density of output, it can be seen that maximum is up to 10mA/m2；（b）Figure is
The current density measured after rectified；（c）Figure be it is rectified after output signal be used for drive 20 green LED lamps, explanation
The energy of waste water in family can be converted directly into electric energy that can be practical by generator provided by the invention；（d）Figure is rectification
Later output signal for 33 μ F commercial power capacity charge, the magnitude of voltage measured, to be charged at three minutes or so
About 1.9V, it was demonstrated that the output electric signal of generator can be really electrical equipment charging used in life, clearly show its application
Potentiality.
Fig. 8 is the situation rained in the continuous water droplet simulating natural environment that is sprayed using shower nozzle in family, herein
The energy of raindrop is effectively collected using the generator system in Fig. 5.（a）Figure is the current density of generator output of the present invention,
Maximum is up to 1.5mA/m2；（b）Figure be it is rectified after output signal be used for drive 20 green LED lamps, illustrate the present invention
The energy of waste water in family can be converted directly into electric energy that can be practical by the generator of offer, and technology of the invention is special in addition
It is not adapted to develop the generator of large area, if the size of generator in Fig. 8 be 15cm × 15cm, for being applied to family in the future
Outer is enormously potential；（c）Figure is the current density of conventional electric generators output, and maximum is up to 0.6mA/m2, also successful presentation
We can more effectively collect the energy of rainwater really；（d）Figure be it is rectified after output come for 33 μ F commercial power capacity charge,
The magnitude of voltage measured, it was demonstrated that the output electric signal of generator can be electrical equipment charging used in life, clearly display really
Go out its application potential.
Accordingly, the present invention also provides a kind of electricity-generating method for collecting working fluid energy, utilizes any one above-mentioned hair
The liquid of motor, electrically charged drop or flowing produces sense with being separated after the upper surface of frictional layer 10, in conducting element 11
Answer electric charge and outwards export electric signal.
Preferably, carry the liquid of drop or flowing after the friction such as liquid-to-air or water wall of drop or flowing
Electric charge, then the upper surface with frictional layer 10, are generated electricity.
In order that liquid surface carries more electric charges, it is preferred that the distance that the friction such as drop or liquid-to-air is passed through
In more than 20cm.
Embodiment：
First, family and industrial wastewater kinetic energy collecting device
Long and wide 5cm, one piece of the polyethylene board that thickness is 0.1cm are taken, and it is equal to plate long and width in its surface
4.5cm, the Copper thin film that thickness is 150nm, are considered as substrate and conducting element.
Using long and width be 5cm hole aluminum oxide as template, pour into dimethyl silicone polymer mixed liquor,
Toasted 1 hour under conditions of 120 DEG C, remove afterwards and can obtain upper surface and possess columnar arrays（Micro-nano structure layer）Poly- diformazan
Radical siloxane film（Frictional layer）.
Conducting element is drawn with wire, next surface is had to the PDMS membrane lower surface of columnar arrays
It is laid on the conducting element covered with dimethyl silicone polymer mixed liquor, is toasted 12 hours under conditions of 60 DEG C, forms hair
Motor.
Generator is placed in the water pipe of family or industrial wastewater flowing, one can be completed and can be used for collecting family in environment
Or the generator of the mobile handling machinery energy of industrial wastewater.It must emphasize herein, this generator can be inserted once more because thickness is minimum
It is individual to collect the mechanical energy of circulating water simultaneously in a water pipe, with up to the purpose effectively utilized.
2nd, wave and waterfall mechanical energy collector
Utilize the hole alumina formwork that size is 30cm × 30cm and equal area, the polytetrafluoroethyl-ne that thickness is 75 μm
Alkene commercial film is pressurizeed 40 minutes under 400 DEG C of high temperature, can be obtained the frictional layer of the polytetrafluoroethylene (PTFE) containing columnar arrays and be rubbed
Wipe the micro-nano structure layer of layer upper surface.Afterwards by this lower surface of poly tetrafluoroethylene containing columnar arrays plate size for 29.5cm ×
29.5cm, the aluminium film that thickness is 100nm connect extraction wire as conducting element on conducting element.Finally make to be coated with
The polyethylene board of aluminium film towards lucite substrate be affixed to size be 30cm × 30cm, thickness be having for 0.6cm
In machine glass substrate, as generator.There is the poly tetrafluoroethylene of columnar arrays using surface, polytetrafluoroethyl-ne can be effectively increased
The hydrophobicity of alkene film, add the pulse signal output performance of generator.
3rd, rainwater energy harvester
The polyethylene terephthalate (PET) that thickness is 5cm × 5cm for 100 μm, size is used to be used as substrate, on its surface
Size is 4.5cm × 4.5cm, thickness is 20nm tin indium oxide (ITO) film is plated as conducting element, and in conducting element
Upper connection extraction wire.
Then it is 50 μm from thickness, and the polydimethylsiloxanefilm film conduct that upper surface has pyramid array rubs
Wipe layer.It is to be rotated first on silicon chip that upper surface, which has the production method of the polydimethylsiloxanefilm film of pyramid array,
Last layer photoresist is coated, the length of side is formed on a photoresist in micron or the square window of secondary micron dimension using the method for photoetching
Mouthful array, then again through overheating the chemical etching of potassium hydroxide, you can form the template of pyramidal depressions array of structures；Afterwards
Dimethyl silicone polymer mixed liquor is poured into template, is toasted 12 hours under conditions of 60 DEG C, is removed again afterwards i.e. available
Upper surface has the polydimethylsiloxanefilm film of pyramid array.This pyramidal dimethyl silicone polymer of tool is thin
The lower surface of film is laid on the conducting element covered with dimethyl silicone polymer mixed liquor, is toasted once again under conditions of 60 DEG C
12 hours formation generators.
In the generator, used substrate, conducting element, frictional layer are high light transmittance material, are extremely suitable for directly putting
The collection of rainwater energy is carried out at the top of building or window, is the technology of a great application prospect.
So far, the multiple embodiments of the present invention are described in detail combined accompanying drawing.According to above description, this area
Technical staff should to the generator based on water contact of the present invention, electricity-generating method with and preparation method thereof have and clearly recognize
Know.
In addition, the implementation for not illustrating or describing in accompanying drawing, is known to a person of ordinary skill in the art in art
Form.And the above-mentioned definition to each element and method is not limited in the various concrete structures mentioned in embodiment or shape
Shape, one of ordinary skill in the art can replace while it is simply known.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail
Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (29)
- A kind of 1. generator for collecting working fluid energy, it is characterised in that including：Conducting element；Frictional layer, the lower surface of the frictional layer cover all conducting element；Separated after the upper surface of electrically charged drop or the liquid of flowing and the frictional layer, the conducting element can Produce charge inducing and outwards export electric signal.
- 2. generator according to claim 1, it is characterised in that the electric charge of the drop or the liquid of flowing institute band comes from The friction of the drop or the liquid and other materials of flowing.
- 3. generator according to claim 1, it is characterised in that the upper surface of the frictional layer is for electroneutral or with electricity Lotus.
- 4. according to the generator described in claim any one of 1-3, it is characterised in that the material of the frictional layer is insulation material Material.
- 5. generator according to claim 4, it is characterised in that the insulating materials selects following one or more：Benzene Amine-formaldehyde resins, polyformaldehyde, ethyl cellulose, polyamide nylon 11, polyamide nylon 66, wool and its fabric, silk and its Fabric, paper, polyethylene glycol succinate, cellulose, cellulose acetate, polyethyleneglycol adipate, poly- phthalic acid two Allyl ester, regenerated cellulosic sponge, cotton and its fabric, polyurethane elastomer, SAN, styrene-fourth two Alkene copolymer, wood, hard rubber, acetate, staple fibre, polymethyl methacrylate, polyvinyl alcohol, polyester, polyisobutene, Elastic polyurethane sponge, polyethylene terephthalate, polyvinyl butyral resin, hycar, neoprene rubber Glue, natural rubber, polyacrylonitrile, poly- (vinylidene chloride-co- acrylonitrile), poly bisphenol carbonic ester, CPPG, poly- inclined two chloroethene Alkene, poly- (2,6- dimethyl polyphenylene oxide), polystyrene, polyethylene, polypropylene, poly- diphenyl propane carbonic ester, poly- Ethylene glycol terephthalate, polyimides, polyvinyl chloride, dimethyl silicone polymer, polytrifluorochloroethylene, polytetrafluoroethylene (PTFE) and Parylene.
- 6. according to the generator described in claim any one of 1-3, it is characterised in that the material of the frictional layer is semiconductor,The semiconductor selects following one or more of materials：The race of silicon, germanium, the IIIth and the Vth compounds of group, the IIth and the VIth Compound, and the solid solution being made up of III-V compounds of group and II-VI compounds of group；Or the material of the frictional layer is selected from manganese, chromium, iron, the oxide of copper, or silica, zinc oxide, BiO2And Y2O3。
- 7. according to the generator described in claim any one of 1-3, it is characterised in that the part or all of upper table of the frictional layer Face includes micro-nano structure layer, and the micro-nano structure layer choosing is from nano wire, nanotube, nano particle, nanometer rods, nano flower, nanometer Groove, micron trenches, nanocone, micron cone, nanosphere and micron chondritic, and the array formed by aforementioned structure.
- 8. generator according to claim 7, it is characterised in that the micro-nano structure layer is straight during the frictional layer to prepare Connect to be formed；Or the micro-nano structure layer is intersperses or coated with nano material layer is formed in the upper surface of frictional layer；Or the micro-nano structure layer is to be prepared by photoengraving, chemical etching or plasma etching in the upper surface of frictional layer.
- 9. generator according to claim 7, it is characterised in that the frictional layer either micro-nano structure layer to be hydrophilic or Hydrophobic structure.
- 10. according to the generator described in claim any one of 1-3, it is characterised in thatThe upper surface of the frictional layer is hydrophobic material, and the liquid is polar liquid；Or the upper surface of the frictional layer is water wetted material, the liquid is nonpolar liquid.
- 11. generator according to claim 10, it is characterised in that polar liquid is water, formic acid, methanol, ethanol, positive third Alcohol, isopropanol, n-butanol, acetic acid, dimethyl sulfoxide (DMSO), dimethylformamide, acetonitrile or acetone；The nonpolar liquid is hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran or dichloromethane.
- 12. according to the generator described in claim any one of 1-3, it is characterised in that the upper surface of the frictional layer or institute State liquid and pass through chemical modification.
- 13. generator according to claim 12, it is characterised in that the chemical modification make the frictional layer upper surface with In the liquid, the functional group for being more easy to betatopic is introduced in polarity is positive material, or, draw in polarity is negative material Enter the functional group for the electronics that is more easy to get；Or the chemical modification makes the frictional layer with the liquid, positive charge is introduced in polarity is positive material；Or Person, negative electrical charge is introduced in polarity is negative material.
- 14. generator according to claim 13, it is characterised in that the functional group for being more easy to betatopic includes：Amino, Hydroxyl or alkoxy；The functional group for being more easy to get electronics includes：Acyl group, carboxyl, nitro or sulfonic group.
- 15. generator according to claim 7, it is characterised in that the micro-nano structure layer of the frictional layer upper surface and institute The material for stating frictional layer is identical.
- 16. according to the generator described in claim any one of 1-3, it is characterised in that the frictional layer is hard material or soft Property material.
- 17. according to the generator described in claim any one of 1-3, it is characterised in that its thickness range of the frictional layer is 50nm~2cm.
- 18. generator according to claim 7, it is characterised in that the thickness of the micro-nano structure layer is between the μ of 20nm~20 Between m.
- 19. according to the generator described in claim any one of 1-3, it is characterised in that also include：Substrate, the conducting element are arranged on the substrate top surface；The frictional layer and the substrate are by the conducting element It is completely covered.
- 20. according to the generator described in claim any one of 1-3, it is characterised in that also include：Substrate, the substrate upper and lower surface set a conducting element respectively；On two conducting elements described in covering Frictional layer.
- 21. generator according to claim 19, it is characterised in that the material of the substrate is hard material or flexible material Material.
- 22. according to the generator described in claim any one of 1-3, it is characterised in that the material choosing of the conducting element uses Metal, conductive oxide or conducting polymer.
- 23. according to the generator described in claim any one of 1-3, it is characterised in that the conducting element is in the friction The lower surface of layer deposits the film to be formed.
- 24. according to the generator described in claim any one of 1-3, it is characterised in that the conducting element be hard material or Flexible material, its thickness is between 10nm~500 μm.
- 25. according to the generator described in claim any one of 1-3, it is characterised in that the conducting element and ground potential or Equipotential source electrically connects.
- 26. according to the generator described in claim any one of 1-3, it is characterised in that the frictional layer, conducting element and substrate It is transparent material.
- A kind of 27. electricity-generating method using any one of the claim 1-26 generators, it is characterised in that electrically charged drop Or the liquid of flowing produces charge inducing and outwards output electricity with being separated after the upper surface of the frictional layer in conducting element Signal.
- 28. electricity-generating method according to claim 27, it is characterised in that the drop or the liquid of flowing pass through friction belt After electricity with the upper surface of the frictional layer.
- 29. electricity-generating method according to claim 28, it is characterised in that the distance of the drop or fluid friction process exists More than 20cm.
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