CN107768510A - A kind of electrothermal module and preparation method thereof - Google Patents
A kind of electrothermal module and preparation method thereof Download PDFInfo
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- CN107768510A CN107768510A CN201610703927.0A CN201610703927A CN107768510A CN 107768510 A CN107768510 A CN 107768510A CN 201610703927 A CN201610703927 A CN 201610703927A CN 107768510 A CN107768510 A CN 107768510A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The invention discloses a kind of electrothermal module and preparation method thereof, is related to nano material technical field of thermoelectric conversion.The electrothermal module includes continuous flexible thermal electric film, there are multiple p-type plane domains that P-type material characteristic is presented and multiple N-type plane domains that n type material characteristic is presented, the bearing of trend of multiple p-type plane domains and multiple N-type plane domains along flexible thermal electric film is continuous and is alternately distributed in it；Wherein, folded form formation one compact structure of the flexible thermal electric film along the bearing of trend to be substantially " W " shape or be wound with same direction, and so that any face each other to adjacent p-type plane domain and N-type plane domain, so as to form corresponding P N statements of account member；And insulation diaphragm, it is arranged between opposed facing the p-type plane domain and N-type plane domain in every P N statement of account members.Present invention also offers corresponding preparation method.Preparation method of the present invention is simple, is formed electrothermal module compact dimensions, better performances.
Description
Technical field
The present invention relates to nano material technical field of thermoelectric conversion, more particularly, to a kind of electrothermal module and its preparation side
Method.
Background technology
The electrothermal module being made up of p-type and N-type thermoelectric material can be directly realized by the mutual conversion of electric energy and heat energy.In temperature
In terms of poor generating, electrothermal module can will effectively result from the heat energy and work of nature thermal source (such as solar energy or geothermal energy)
Industry, the used heat for generally existing of living are converted directly into valuable electric energy, realize recycling for the energy.In thermoelectric cooling side
Face, compared to conventional chiller, thermoelectric cooling will reduce the use of poisonous chlorofluorination hydrocarbon and its substitute, and reduce system
Weight, cost and the energy resource consumption of cooler.Meanwhile thermoelectric module architecture is simple, work when there is no the mechanical component of motion, also not
Liquid, the gas medium of danger are needed, therefore quieter operation, noiseless, stability are high and will not bring pollution.It is dirty in environment
Today of dye and energy crisis getting worse, before electrothermal module has a wide range of applications in the field such as thermo-electric generation and thermoelectric cooling
Scape and very strong realistic meaning.
The content of the invention
Inventor has found, reports that more electrothermal module has by polymer, CNT, carbon nano-tube/polymer at present
The flexible electrothermal module that composite is formed.Need to prepare p-type and N-type thermoelectricity respectively when preparing the flexible electrothermal module
Leg, it is then by metal contact wires that the progress of these thermoelectricity legs is electrically coupled in series, in addition, in order to reduce metal contact wires and thermoelectricity leg
Contact resistance, it will usually tens nanometers of golden or silver-colored top electrode is deposited on every thermoelectricity leg or spreads silver on thermoelectricity leg
Glue.In this way, not only preparation process is cumbersome for electrothermal module, and size is also not compact enough, and inventor also found, when the thermoelectricity mould
When block contacts with thermal source, due to the interval between thermoelectricity leg, these intervals can be caused can not to utilize thermal source, so as to limit to heat
The utilization in source.
Meanwhile inventor, it has furthermore been found that in some current reports, such as Crispin seminar in 2011 utilizes excellent
As p-type thermoelectricity leg, TTF-TCNQ is prepared for complete containing 54 thermoelectricity legs as n-type thermoelectricity leg the PEDOT-Tos films of change
Organic electrothermal module, its power density is 0.27 μ W cm under 30K thermograde-2(power density is power divided by whole mould
The cross-sectional area of block).Metal coordinating polymer poly [Na of the Zhu seminar in 2012 based on n-typex] and p-type (Ni-ett)
Metal coordinating polymer poly [Cux(Cu-ett) the full stress-strain thermoelectricity mould containing 35 pairs of thermocouples] is prepared on Al substrates
Block, power density is 2.8 μ W cm under 30K thermograde-2.Bazan seminar in 2015 utilizes conjugated polyelectrolytes/mono-
Wall carbon nano tube (CPE/SWNT) laminated film is prepared for the radial direction electrothermal module containing 8 thermoelectricity legs, it is possible to achieve to a heat
The utilization in source, caused watt level is 0.3nW under 35K thermograde.The power output of wherein flexible electrothermal module and
The less reason of power density is not high because of the p-type or the power factor of the flexible thermoelectric material of N-type for forming module, therefore greatly
The big conversion efficiency of thermoelectric that have impact on module.
Therefore, it is an object of the invention to provide a kind of electrothermal module, the preparation method of the electrothermal module is simple, size is tight
Gather, performance it is higher, there is larger power output and power density.
It is another object of the present invention to provide a kind of preparation method of electrothermal module, the preparation method is simple to operate,
Prepared electrothermal module compact dimensions, performance are higher, have larger power output and power density.
Especially, the invention provides a kind of electrothermal module, including：
Continuous flexible thermal electric film, there are multiple p-type plane domains that P-type material characteristic is presented in it and N-type is presented
Multiple N-type plane domains of material property, the multiple p-type plane domain and the multiple N-type plane domain are along the flexibility
The bearing of trend of thermal electric film is continuous and is alternately distributed；Wherein, the flexible thermal electric film along the bearing of trend with substantially
For " W " shape folded form formed a compact structure, or the flexible thermal electric film along the bearing of trend with same direction
The folded form of winding forms a compact structure, and causes any mutual to adjacent p-type plane domain and N-type plane domain
Face, so as to form corresponding P-N junction unit；And
Insulation diaphragm, be arranged on opposed facing p-type plane domain and N-type plane domain in each P-N junction unit it
Between.
Further, each p-type plane domain and each N-type plane domain have essentially identical area and
Shape, to enable adjacent the p-type plane domain and N-type plane domain of the flexible thermal electric film substantially overlapped, and
And make the area on the main surface of the compact structure for each N-type plane domain or the area of p-type plane domain.
Further, the insulation diaphragm has essentially identical with the p-type plane domain and the N-type plane domain
Area and shape.
Further, the insulation diaphragm is flexible.
Further, the insulation diaphragm is heat-insulated.
Further, in addition to two electrodes for transmitting telecommunication number, described two electrodes are located at the flexibility respectively
Thermal electric film extends along the both ends in direction, and the part extended by the both ends forms；Alternatively, described two electrodes are
The flexible thermal electric film extends along the double-end external electrode in direction, the dispatch from foreign news agency extremely flexibility or non-flexible.
Further, the flexible thermal electric film is that partial modification is carried out on a flexible foundation film to form the P
Type plane domain and/or the N-type plane domain；Alternatively, the flexible foundation film is continuous carbon nano-tube network, carbon
Nano-tube film, graphene film, two-dimentional organic conductive network or two-dimentional electroconductive organic film, two-dimensional ultrathin inorganic conductive network
Or two-dimensional ultrathin inorganic conductive film.
Further, the material of the insulation diaphragm be selected from pet film, Kapton,
One or more in polydimethylsiloxanefilm film, polymethyl methacrylate film, polyvinyl acetate ester film；Or
The insulation diaphragm is the film with insulating barrier, and alternatively, the material of the insulating barrier is Si3N4Or SiO2。
Especially, present invention also offers a kind of preparation method of electrothermal module, including：
There is provided one be in deployed condition flexible foundation film, its have upper surface and it is relative with the upper surface under
Surface；
Formed in the flexible foundation film with multiple p-type plane domains that P-type material characteristic is presented and N-type is presented
Multiple N-type plane domains of material property are to form flexible thermal electric film, the multiple p-type plane domain and the multiple N-type
Bearing of trend of the plane domain along the flexible thermal electric film is continuous and is alternately distributed；
It is covered each by the upper surface of the flexible thermal electric film in the deployed condition and the lower surface
Corresponding first insulation diaphragm and the second insulation diaphragm；Alternatively, first insulation diaphragm and the second insulation diaphragm are flexible
's；
By the flexible thermal electric film together with first insulation diaphragm and second insulation diaphragm along the extension
Direction is folded into a compact structure in the form of being substantially " W " shape or in the form of same direction is wound so that any right
Adjacent p-type plane domain and N-type plane domain faces each other, and by first insulation diaphragm or second insulation diaphragm
They are spaced apart, so as to form corresponding P-N junction unit.
Further, the p-type plane domain and/or the N-type plane domain are by the flexible foundation film
It is upper to carry out partial modification to be formed.
Further, first insulation diaphragm and/or second insulation diaphragm in the multiple p-type plane domain and
Continuously extend on the multiple N-type plane domain.
Further, first insulation diaphragm is more than the first individual diaphragm section separated each other, individual barrier film more than described first
Section is covered each by corresponding the multiple p-type plane domain or corresponding the multiple N-type plane domain.
Further, the multiple p-type plane domain or right corresponding to being covered each by more than described first individual diaphragm sections
It is unlapped described soft to its using more than described first individual diaphragm sections as mask after the multiple N-type plane domain answered
Property basis film region carry out the partial modification, to obtain the multiple N-type plane domain or the multiple p-type plane
Region.
Further, second insulation diaphragm is more than the second individual diaphragm section separated each other, individual barrier film more than described second
Section is covered each by corresponding the multiple p-type plane domain or corresponding the multiple N-type plane domain.
Further, in addition to：Before the folding is carried out, there is provided described for two electrodes of transmitting telecommunication number
Two electrodes extend along the both ends in direction, and the part group extended by the both ends positioned at the flexible thermal electric film respectively
Into；Alternatively, described two electrodes are that the flexible thermal electric film extends along the double-end external electrode in direction, the dispatch from foreign news agency
It is extremely flexible or non-flexible.
Further, the flexible foundation film be continuous carbon nano-tube network, carbon nano-tube film, graphene film,
Two-dimentional organic conductive network or two-dimentional electroconductive organic film, two-dimensional ultrathin inorganic conductive network or two-dimensional ultrathin inorganic conductive are thin
Film.
Further, the material of the insulation diaphragm be selected from pet film, Kapton,
One or more in polydimethylsiloxanefilm film, polymethyl methacrylate film, polyvinyl acetate ester film；Or
The insulation diaphragm is the film with insulating barrier, and alternatively, the material of the insulating barrier is Si3N4Or SiO2。
Inventor has found, is put down by forming continuous and alternatively distributed p-type plane domain and N-type in flexible foundation film
Face region, and the electrothermal module is formed by folding, not only preparation method simple possible, and the electrothermal module chi formed
It is very little it is compact, thermal source, better performances can be made full use of, power output can be greatly improved, while power density is also larger.
Brief description of the drawings
Some specific embodiments of the present invention are described in detail by way of example, and not by way of limitation with reference to the accompanying drawings hereinafter.
Identical reference denotes same or similar part or part in accompanying drawing.In accompanying drawing：
Structural representation when Fig. 1 is the electrothermal module expansion according to one embodiment of the invention；
Fig. 2 is along the diagrammatic cross-section of c-c lines in Fig. 1；
Fig. 3 is the rough schematic view of Fig. 2 " W " shape folded form；
Fig. 4 is the rough schematic view of Fig. 2 winding folded form；
Fig. 5 is the schematic flow sheet that Fig. 1 is folded into electrothermal module；
Fig. 6 is the schematic flow sheet according to the electrothermal module preparation method of one embodiment of the invention；
The rough schematic that it is in " W " shape form during the electrothermal module expansion according to another embodiment of the present invention that Fig. 7, which is,；
The rough schematic that it is in " W " shape form during the electrothermal module expansion according to yet another embodiment of the invention that Fig. 8, which is,；
The rough schematic that it is in " W " shape form during the electrothermal module expansion according to other embodiments of the invention that Fig. 9, which is,；
Figure 10 is voltage output figure of the flexible electrothermal module under different steady state temperature differences in embodiment 1；
Figure 11 is that the flexible electrothermal module in embodiment 1 is 330K in hot-side temperature, the electric piezo-electric when temperature difference is 27.5K
Flow curve and power-current curve map.
Embodiment
In an embodiment of the invention, as shown in figure 1, the electrothermal module includes continuous flexible thermal electric film 12,
There are multiple p-type plane domains 15 that P-type material characteristic is presented and multiple N-type plane domains that n type material characteristic is presented in it
16, the bearing of trend of the multiple p-type plane domain 15 and the multiple N-type plane domain 16 along the flexible thermal electric film 12
Continuously and it is alternately distributed；It is appreciated that Fig. 1 show the three-dimensional structure diagram when electrothermal module deploys, it not only has edge
The length and width of plane, also there is the thickness for going deep into internal plane.Wherein, the flexible thermal electric film 12 is along the extension side
To be substantially that the folded form of " W " shape forms a compact structure, or the flexible thermal electric film along the bearing of trend
One compact structure is formed with the folded form of same direction winding, as shown in Fig. 2, Fig. 3, Fig. 4 and Fig. 5, and it is so that any right
Adjacent p-type plane domain 15 and N-type plane domain 16 faces each other, so as to form corresponding P-N junction unit；And insulation every
Film, it is arranged between opposed facing the p-type plane domain 15 and N-type plane domain 16 in each P-N junction unit.
Herein, the P-type material can be p-type semiconductor material, and the n type material can be N-type semiconductor material.
The bearing of trend of the multiple p-type plane domain 15 and the multiple N-type plane domain 16 along the flexible thermal electric film 12 connects
In continuing and being alternately distributed " continuous ", refer between each p-type plane domain 15 and each N-type plane domain 16 it being not to be spaced
's.Fig. 4 is schematically illustrated in direction as shown, and flexible thermal electric film 12 is formed along upper right side with the folded form wound
Cramped construction.Meanwhile the insulation diaphragm can include the first insulation diaphragm 14 and the second insulation diaphragm 11.
Further, to make the compact dimensions of the electrothermal module, each p-type plane domain 15 and each N
Type plane domain 16 has essentially identical area and shape, to cause the adjacent p-type plane area of the flexible thermal electric film 12
Domain 15 and N-type plane domain 16 can be substantially overlapped, and make the area on the main surface of the compact structure to be each
The area of the N-type plane domain 16 or p-type plane domain 15.In this way, would not cause there is interval in the electrothermal module, because
And thermal source can be made full use of.
Meanwhile as shown in figure 1, the insulation diaphragm has and the p-type plane domain 15 and the N-type plane domain 16
Essentially identical area and shape.The insulation diaphragm can be it is flexible, so, it is possible to so that insulation diaphragm fold when
Folding is easily deformed, can also make insulation diaphragm is more docile to be covered at p-type plane domain 15 or N-type plane domain 16.Together
When, the insulation diaphragm can also be heat-insulated.
Further, as shown in figure 1, the electrothermal module can also include two electrodes 130 for transmitting telecommunication number,
Described two electrodes extend along the both ends in direction positioned at the flexible thermal electric film 12 respectively, and extended by the both ends
Part forms；Alternatively, described two electrodes 130 are that the flexible thermal electric film 12 extends along the double-end dispatch from foreign news agency in direction
Pole, to make electrode 130 be attached to the both ends of the flexible thermal electric film 12 with transmitting telecommunication number, the flexible thermal electric film 12
Both ends the electrode 130 is pasted using elargol 131.The external electrode 130 can be flexible, as flexible wire CNT is fine
Dimension, in this way, the electrothermal module then formed depends on beneficial to carrying and easily other body surfaces etc. integrally in flexibility.It is described
External electrode can also be non-flexible, and such as silver wire and copper conductor, in this way, then electrothermal module is in flexible, only electrode is in non-flexible,
Beneficial to the detection of signal.
Further, the flexible thermal electric film 12 is that progress partial modification is described to be formed on a flexible foundation film
P-type plane domain 15 and/or the N-type plane domain 16；Alternatively, the flexible foundation film can be continuous carbon nanometer
Managed network, carbon nano-tube film, graphene film, two-dimentional organic conductive network or two-dimentional electroconductive organic film, two-dimensional ultrathin without
Machine conductive network or two-dimensional ultrathin inorganic conductive film.
In an embodiment of the invention, the material of the insulation diaphragm is selected from polyethylene terephthalate (PET)
It is film, polyimides (PI) film, dimethyl silicone polymer (PDMS) film, polymethyl methacrylate (PMMA) film, poly-
One or more in vinylacetate (PVA) film；First insulation diaphragm 14 and second insulation diaphragm 11 every
Membrane material can be with identical, can also be different.It is alternatively, described or the insulation diaphragm can be the film with insulating barrier
The material of insulating barrier can be Si3N4Or SiO2。
Particularly, present invention also offers a kind of preparation method of electrothermal module, as shown in fig. 6, its can include it is as follows
Step：
S100, there is provided one be in deployed condition flexible foundation film, its have upper surface and with the upper surface phase
To lower surface；
S200, formed with multiple p-type plane domains that P-type material characteristic is presented in the flexible foundation film and be in
Multiple N-type plane domains of existing n type material characteristic are to form flexible thermal electric film, the multiple p-type plane domain and described more
Bearing of trend of the individual N-type plane domain along the flexible thermal electric film is continuous and is alternately distributed；
S300, distinguish in the upper surface of the flexible thermal electric film in the deployed condition and the lower surface
First insulation diaphragm corresponding to covering and the second insulation diaphragm；Alternatively, first insulation diaphragm and the second insulation diaphragm are
Flexible；
S400, by the flexible thermal electric film together with first insulation diaphragm and second insulation diaphragm along described
Bearing of trend is folded into a compact structure in the form of being substantially " W " shape or in the form of same direction is wound so that appoints
A pair adjacent p-type plane domains and N-type plane domain face each other, and by first insulation diaphragm or second insulation
They are spaced apart by barrier film, so as to form corresponding P-N junction unit.
In an embodiment of the invention, situation is prepared according to actual, can be by step S200 and step S300 order
Exchange, in this way, after the upper and lower surface of flexible foundation film is covered each by insulation diaphragm, the insulation diaphragm can be with
Used as mask plate, when being modified to flexible foundation film, the part covered by mask plate keeps flexible foundation film
P-type characteristic, and the part not covered by mask plate can be then modified so that the part present N-type characteristic.Certainly, in order to
The p-type or N-type characteristic that the prominent flexible thermal electric film 12 possesses in itself, before mask film covering version, locate after can also using
The method of reason so that p-type or the N-type characteristic is further strengthened, and the performance of electrothermal module is improved with this.
Specifically, the p-type plane domain and/or the N-type plane domain are by the flexible foundation film
Partial modification is carried out to be formed.As shown in fig. 7, first insulation diaphragm 14 and/or second insulation diaphragm 11 can be with
Continuously extend on the multiple p-type plane domain and the multiple N-type plane domain.As shown in Figure 8 and Figure 9, described first
Insulation diaphragm 14 is more than the first individual diaphragm sections separated each other, and individual diaphragm section more than described first is covered each by corresponding the multiple
P-type plane domain or corresponding the multiple N-type plane domain.Fig. 7, Fig. 8 and Fig. 9 are shown with " W " shape folded form
The distributing position of flexible thermal electric film 12 and insulation diaphragm, it will be understood that with the soft of the folded form that winds in the same direction
The distributing position of insulation diaphragm at property thermal electric film 12 can also be distributed as shown in Figure 7 and Figure 8, it is also understood that
, in folding process, as long as having insulation diaphragm between opposed facing p-type plane domain and N-type plane domain, then should
The distribution mode of kind insulation diaphragm is just allowed.
By setting insulation diaphragm, it is possible to prevent when flexible thermal electric film 12 folds, prevent p type island region domain and N
Type region is in contact.Thus, after folding, whole inside modules are formed the knot that p type island region domain and N-type region domain are in series
Structure.When module works, it is possible to which caused voltage superposition is got up after each region is applied into the temperature difference.If be not provided with insulation every
Film, then when flexible thermal electric film 12 folds, p type island region domain and N-type region domain will plane-plane contact, it is overall after folding
Being equivalent to one piece has certain thickness conductor, and on the one hand this structure can substantially reduce the voltage of final output, the opposing party
The p type island region domain and N-type region domain that face modification area is formed with unmodified region are in contact, modified material present on modification area
The property in unmodified region can also be changed, as N-type region domain and p type island region domain contact, it is possible to remaining doping on N-type region domain
The p-type in p type island region domain can be weakened or be changed into N-type by agent, in this case, can also influence final output to a certain extent
Voltage.
In an embodiment of the invention, the multiple p-type corresponding to being covered each by more than described first individual diaphragm sections is put down
After face region or corresponding the multiple N-type plane domain, using more than described first individual diaphragm sections as mask, to it not
The region of the flexible foundation film of covering carries out the partial modification, to obtain the multiple N-type plane domain or institute
State multiple p-type plane domains.Herein, the modification can be included in droplet casting, spin coating, spray at the flexible thermal electric film 12
Painting, printing, thermal evaporation, electron beam evaporation, vapour deposition or magnetron sputtering N-type or P-type dopant are to form N-type or p type island region domain.
Further, as shown in Fig. 8 or Fig. 9, second insulation diaphragm 11 is more than the second individual diaphragm sections separated each other,
Individual diaphragm section more than described second is covered each by corresponding the multiple p-type plane domain or corresponding the multiple N-type plane
Region.
In an embodiment of the invention, before the folding is carried out, there is provided for two electrodes of transmitting telecommunication number,
Described two electrodes extend along the both ends in direction, and the portion extended by the both ends positioned at the flexible thermal electric film respectively
It is grouped into；Alternatively, described two electrodes are that the flexible thermal electric film extends along the double-end external electrode in direction, described
It is dispatch from foreign news agency extremely flexibility or non-flexible.
By forming continuous and alternatively distributed p-type plane domain and N-type plane domain in flexible foundation film, and lead to
Cross folding and form the electrothermal module, not only preparation method simple possible, and formed electrothermal module compact dimensions, can
Thermal source, better performances are made full use of, power output can be greatly improved, while power density is also larger.
Beneficial effects of the present invention are further illustrated with reference to more specifically embodiment.
Embodiment 1：Large area p-type carbon nano-tube film and N type dopant based on direct growth prepare flexible thermoelectricity mould
Block.
S100, utilize improved floating catalytic chemical vapour deposition technique direct growth large area carbon nano-tube film, performance
It is substantially better than the carbon nano-tube film prepared by dispersing Nano carbon tubes solution.Original carbon nanotubes film is due to oxygen in air
Doping shows p-type characteristic；
S200, CNT band (i.e. flexible thermal electric film 12) is cut out from large area carbon nano-tube film and is placed on
On PET substrate, PET substrate covers all whole carbon nano-tube film as the second insulation diaphragm 11.In CNT band
Upper some PET double faced adhesive tapes of adhesion spaced apart make it be in close contact with band as the first insulation diaphragm 14, pressing；
S300, it is stained with flexible wire carbon nano-tube fibre by the use of elargol 131 at CNT band both ends and is used as electrode 130
In extraction electric signal；
S400, in the region that CNT band does not block liquid-transfering gun droplet casting N type dopant (1wt.% polyethyleneimine
Amine aqueous solution), then dried 5 minutes at 50 DEG C.Then CNT bar takes the region blocked by PET double faced adhesive tapes 14 and keeps p-type,
The region do not blocked is doped to N-type, CNT bar take quickly form continuous and alternatively distributed p-type plane domain and
N-type plane domain；
S500, CNT band is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Form the electrothermal module of flexible continuous type.
One end of the above-mentioned flexible electrothermal module prepared is heated, then along direction in face, the both ends meeting of module
Produce a thermograde (Δ T=Thot-Tcold), due to Seebeck effect, significant thermal voltage will produce therewith.
Figure 10 is voltage output figure of the flexible electrothermal module under different steady state temperature differences, as shown in Figure 10, with module two
The increase of the temperature difference is held, caused voltage also linearly increases, and passes through linear fit slope of a curve, it can be deduced that the flexible thermoelectricity mould
Block has larger thermo-electromotive force：410μV K-1。
During the power output of general test room temperature electrothermal module, the temperature difference, which is chosen at 30K or so and compared, reference value, because
The temperature difference less than 30K easily obtains from natural environment, and it is 330K that Figure 11, which is flexible electrothermal module in hot-side temperature, the temperature difference
For 27.5K when voltage-current curve and power-current curve map.As can be drawn from Figure 11, the flexible electrothermal module has
Small internal resistance R0=12.5 Ω, open-circuit voltage VocFor 11.3mV, short circuit current IscFor 0.9mA, maximum power output is 2.51 μ
W, power density are 167 μ W cm-2(power density is calculated by the cross-sectional area of power divided by whole module, is included
The thickness of PET double faced adhesive tape barrier films).It was found from above analysis result, the performance of the flexible electrothermal module will be substantially better than to be reported before
Performance of the flexible thermo-electric device in road under similar temperature differentials.
Embodiment 2：The carbon nano-tube film and N type dopant system that the carbon nano-tube solution disperseed based on p-type is prepared
Standby flexible electrothermal module.
S100, it is filtered by vacuum scattered carbon nano-tube solution and large area carbon nano-tube film is prepared.Equally, without place
The CNT of reason can show p-type characteristic due to the doping of oxygen in air；
S200, large area carbon nano-tube film is soaked 5 hours in concentrated nitric acid, then rinsed repeatedly with deionized water,
So that the p-type characteristic of original carbon nanotubes film is strengthened.After drying, set and cover on the selection area of carbon nano-tube film
Film version, N type dopant (2wt.% benzyl viologen solution) is sprayed on the region that mask plate does not block, is then dried at 60 DEG C
It is dry 10 minutes.The region then blocked on carbon nano-tube film by mask plate keeps p-type, and the region do not blocked is doped to N-type, carbon
Continuous and alternatively distributed p-type plane domain and N-type plane domain are quickly formd on nano-tube film；
S300, it is stained with silver wire with elargol at carbon nano-tube film both ends and is used to draw electric signal；
S400, as shown in figure 8, being received in the carbon for foring continuous and alternatively distributed p-type plane domain and N-type plane domain
PDMS film is set only to cover N-type plane domain as the second insulation diaphragm below mitron film；It is thin that top is also provided with PDMS
Film only covers p-type plane domain as the first insulation diaphragm；
S500, carbon nano-tube film is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Form the electrothermal module of flexible continuous type.
Embodiment 3：The graphene film and N type dopant prepared based on scattered redox graphene solution prepares soft
Property electrothermal module.
Large-area graphene plural layers are prepared in S100, the scattered redox graphene solution of spin coating.Original
Graphene plural layers can show p-type characteristic；
S200, mask plate is set on the selection area of large-area graphene plural layers, in the area that mask plate does not block
Thermal evaporation alkali metal potassium, potassium have strong reducing property on domain, can be as the N type dopant of graphene.Then large-area graphene multilayer
The region blocked on film by mask plate keeps p-type, and the region do not blocked is doping to N-type by potassium, shape on graphene plural layers
Into continuous and alternatively distributed p-type plane domain and N-type plane domain；
S300, extend a part at the both ends of large-area graphene plural layers and be used to draw electric signal as electrode；
S400 is more in the large-area graphene for foring continuous and alternatively distributed p-type plane domain and N-type plane domain
PVA film is set only to cover N-type plane domain as the second insulation diaphragm below layer film；Top sets PI film conducts
First insulation diaphragm, only cover p-type plane domain；
S500, large-area graphene is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Plural layers form the electrothermal module of flexible continuous type.
Embodiment 4：P-type graphene film and N type dopant based on direct growth prepare flexible electrothermal module.
S100, using floating catalytic chemical vapour deposition technique can on copper foil direct growth large-area graphene film；
S200, large-area graphene film is transferred on PDMS substrates from copper foil, PDMS substrates are as the second insulation
Barrier film, cover all whole graphene film；Some PMMA films of adhesion spaced apart, PMMA on graphene film
Film is as the first insulation diaphragm；
S300, it is stained with copper conductor with elargol at large-area graphene film both ends and is used to draw electric signal；
S400, in the region that large-area graphene film is not blocked inkjet printing N type dopant (5wt.% triphenyl
Phosphine solution), then dried 5 minutes at 60 DEG C.The region then blocked in large-area graphene film by PMMA films keeps P
Type, the region do not blocked are doped to N-type, and continuous and alternatively distributed p-type is quickly formd in large-area graphene film and is put down
Face region and N-type plane domain
S500, large-area graphene is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Film forms the electrothermal module of flexible continuous type.
Embodiment 5：N type carbon nanotube film and P-type dopant based on direct growth prepare flexible electrothermal module.
S100, heteroatom source of the gas is led to during chemical vapor deposition, can the side wall of CNT introduce N or
P atoms, the n type carbon nanotube film of large area is prepared；
S200, large area cnt multilayer film is placed on canvas lining bottom, canvas lining bottom as second insulation every
Film, cover all whole carbon nano-tube film；SiN is deposited on selection area on carbon nano-tube filmxBarrier bed, as
One insulation diaphragm；
S300, extend a part at the both ends of large area carbon nano-tube film and be used to draw electric signal as electrode；
S400, in the region droplet casting P-type dopant (30wt.% hydrogenperoxide steam generator) that carbon nano-tube film does not block,
Then dried 5 minutes at 50 DEG C.Then by SiN on carbon nano-tube filmxThe position blocked keeps N-type, the position quilt not blocked
P-type is doping to, continuous and alternatively distributed p-type plane domain and N-type plane domain are quickly formd on carbon nano-tube film
S500, carbon nano-tube film is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Form the electrothermal module of flexible continuous type.
Embodiment 6：Carbon nano-tube film after two steps modification degassing processing prepares flexible electrothermal module.
S100, large area carbon nano-tube film prepared by floating catalytic chemical vapour deposition technique is put into glove box, it is right
It carries out ultraviolet light irradiation so that the oxygen desorption adsorbed on CNT, then the large area carbon nano-tube film after handling
Without p-type and N-type characteristic；
S200, the large area carbon nano-tube film after processing is placed on elastic silk stocking substrate, elastic silk stocking are as
Two insulation diaphragms, cover all whole carbon nano-tube film；Set and cover on the selection area of large area carbon nano-tube film
Film version, droplet casting P-type dopant (the 10M salpeter solution) on the region that mask plate does not block, 5 points are then dried at 50 DEG C
Clock, the then region that mask plate does not block are doped to p-type；
S300, PET double faced adhesive tapes are then covered on p-type plane domain, PET double faced adhesive tapes are as the first insulation diaphragm.Remove
The mask plate set before, droplet casting N type dopant (1wt.% polyethylenimine solution) on the region blocked in s 200, so
Dried 5 minutes at 50 DEG C afterwards, continuous and alternatively distributed p-type plane domain and N-type are formd on subsequent carbon nano-tube film
Plane domain；
S400, it is stained with carbon nano-tube fibre with elargol at the both ends of large area carbon nano-tube film and is used to draw electric signal；
S500, carbon nano-tube film is repeatedly folded by the connecting line along the p-type plane domain and N-type plane domain
Form the electrothermal module of flexible continuous type.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention
Example property embodiment, still, still can be direct according to present disclosure without departing from the spirit and scope of the present invention
It is determined that or derive many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognized
It is set to and covers other all these variations or modifications.
Claims (15)
1. a kind of electrothermal module, including：
Continuous flexible thermal electric film, there are multiple p-type plane domains that P-type material characteristic is presented in it and n type material is presented
Multiple N-type plane domains of characteristic, the multiple p-type plane domain and the multiple N-type plane domain are along the flexible thermoelectricity
The bearing of trend of film is continuous and is alternately distributed；Wherein, the flexible thermal electric film along the bearing of trend be substantially " W "
The folded form of shape forms a compact structure, or the flexible thermal electric film is wound along the bearing of trend with same direction
Folded form formed a compact structure, and cause it is any adjacent p-type plane domain and N-type plane domain are faced each other,
So as to form corresponding P-N junction unit；And
Insulation diaphragm, it is arranged between opposed facing the p-type plane domain and N-type plane domain in each P-N junction unit.
2. electrothermal module according to claim 1, it is characterised in that each p-type plane domain and each N-type
Plane domain has essentially identical area and shape, to cause the adjacent p-type plane domain of the flexible thermal electric film and N-type
Plane domain can be substantially overlapped, and makes the area on the main surface of the compact structure be each N-type plane
Region or the area of p-type plane domain.
3. electrothermal module according to claim 2, it is characterised in that the insulation diaphragm has and the p-type plane area
Domain and the essentially identical area of the N-type plane domain and shape.
4. according to the electrothermal module any one of claim 1-3, it is characterised in that the insulation diaphragm is flexible.
5. according to the electrothermal module any one of claim 1-4, it is characterised in that the insulation diaphragm is heat-insulated.
6. according to the electrothermal module any one of claim 1-5, it is characterised in that also include for transmitting telecommunication number
Two electrodes, described two electrodes extend along the both ends in direction positioned at the flexible thermal electric film respectively, and by the both ends
The part composition extended；Alternatively, described two electrodes are that to extend along direction double-end for the flexible thermal electric film
External electrode, it is the dispatch from foreign news agency extremely flexibility or non-flexible.
7. according to the electrothermal module any one of claim 1-6, it is characterised in that the flexible thermal electric film is one
Partial modification is carried out on flexible foundation film to form the p-type plane domain and/or the N-type plane domain；Alternatively,
The flexible foundation film be continuous carbon nano-tube network, carbon nano-tube film, graphene film, two-dimentional organic conductive network or
Two-dimentional electroconductive organic film, two-dimensional ultrathin inorganic conductive network or two-dimensional ultrathin inorganic conductive film.
8. according to the electrothermal module any one of claim 1-7, it is characterised in that the material of the insulation diaphragm is selected from
Pet film, Kapton, polydimethylsiloxanefilm film, polymethyl methacrylate are thin
One or more in film, polyvinyl acetate ester film；Or
The insulation diaphragm is the film with insulating barrier, and alternatively, the material of the insulating barrier is Si3N4Or SiO2。
9. a kind of preparation method of electrothermal module, including：
A flexible foundation film for being in deployed condition is provided, it has upper surface and the following table relative with the upper surface
Face；
Formed in the flexible foundation film with multiple p-type plane domains that P-type material characteristic is presented and n type material is presented
Multiple N-type plane domains of characteristic are to form flexible thermal electric film, the multiple p-type plane domain and the multiple N-type plane
Bearing of trend of the region along the flexible thermal electric film is continuous and is alternately distributed；
It is covered each by the upper surface of the flexible thermal electric film in the deployed condition and the lower surface correspondingly
The first insulation diaphragm and the second insulation diaphragm；Alternatively, first insulation diaphragm and the second insulation diaphragm are flexible；
By the flexible thermal electric film together with first insulation diaphragm and second insulation diaphragm along the bearing of trend
A compact structure is folded into the form of being substantially " W " shape or in the form of same direction is wound so that any to adjacent
P-type plane domain and N-type plane domain face each other, and by first insulation diaphragm or second insulation diaphragm by it
Be spaced apart, so as to P-N junction unit corresponding to being formed.
10. preparation method according to claim 9, it is characterised in that the p-type plane domain and/or the N-type plane
Region is formed by carrying out partial modification on the flexible foundation film.
11. preparation method according to claim 10, it is characterised in that first insulation diaphragm and/or described second
Insulation diaphragm continuously extends on the multiple p-type plane domain and the multiple N-type plane domain.
12. preparation method according to claim 11, it is characterised in that first insulation diaphragm is the separated each other
Individual diaphragm section more than one, individual diaphragm section more than described first are covered each by corresponding the multiple p-type plane domain or corresponding institute
State multiple N-type plane domains.
13. preparation method according to claim 12, it is characterised in that be covered each by pair in more than described first individual diaphragm sections
After the multiple p-type plane domain or corresponding the multiple N-type plane domain answered, by more than described first individual diaphragm sections
As mask, the partial modification is carried out to the region of its unlapped flexible foundation film, to obtain the multiple N
Type plane domain or the multiple p-type plane domain.
14. the preparation method according to claim 10 or 12, it is characterised in that second insulation diaphragm is to separate each other
More than second individual diaphragm sections, individual diaphragm section more than described second be covered each by corresponding to the multiple p-type plane domain or correspondingly
The multiple N-type plane domain.
15. according to the preparation method any one of claim 10-14, it is characterised in that also include：Carrying out the folding
Before folded, there is provided for two electrodes of transmitting telecommunication number, described two electrodes respectively positioned at the flexible thermal electric film along its
The both ends of bearing of trend, and the part extended by the both ends forms；Alternatively, described two electrodes are the flexible thermoelectricity
Film extends along the double-end external electrode in direction, the dispatch from foreign news agency extremely flexibility or non-flexible.
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