CN107154282A - Multilayer conductive elastic composite - Google Patents

Multilayer conductive elastic composite Download PDF

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Publication number
CN107154282A
CN107154282A CN201610121247.8A CN201610121247A CN107154282A CN 107154282 A CN107154282 A CN 107154282A CN 201610121247 A CN201610121247 A CN 201610121247A CN 107154282 A CN107154282 A CN 107154282A
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CN
China
Prior art keywords
layer
substrate
elastic composite
cnt
conductive
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Pending
Application number
CN201610121247.8A
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Chinese (zh)
Inventor
刘遵峰
贾凤美
吕伟
陈学成
房少立
雷伊鲍曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHANGZHOU TANYU NANO SCIENCE & TECHNOLOGY Co Ltd
JIANGNAN GRAPHENE RESEARCH INSTITUTE
Original Assignee
CHANGZHOU TANYU NANO SCIENCE & TECHNOLOGY Co Ltd
JIANGNAN GRAPHENE RESEARCH INSTITUTE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by CHANGZHOU TANYU NANO SCIENCE & TECHNOLOGY Co Ltd, JIANGNAN GRAPHENE RESEARCH INSTITUTE filed Critical CHANGZHOU TANYU NANO SCIENCE & TECHNOLOGY Co Ltd
Priority to CN201610121247.8A priority Critical patent/CN107154282A/en
Publication of CN107154282A publication Critical patent/CN107154282A/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/544—Torsion strength; Torsion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides the structure and preparation method of a kind of multilayer conductive elastic composite.Above-mentioned multilayer conductive elastic composite, it, which is constituted, includes dielectric layer and conductive layer, and preparation method is that conductive layer and dielectric replace laying composition in substrate.The composite has good tensility and electric conductivity simultaneously, and resistance variations are less than 2% in the case of simple tension 400%；And Reusability more than 2000 times, performance degradation realizes ultra large deformation and the stable electrically conductive elastic composite of performance still less than 5%, really.

Description

Multilayer conductive elastic composite
Technical field
The present invention relates to that can draw refreshing person in electronics, saying more precisely is related to a kind of multilayer conductive elastic composite.
Background technology
In recent years, the development of flexible conducting material is received more and more attention.Leading with large deformation and resistance stabilization Electric elastomeric material, is the key for developing the stretchable circuit of high-performance and electronic device.However, big tensile deformation and holding resistance It is stable, it is two conflicting and opposition factors.Rigid material generally has excellent and stable electric property, but can Tensile property is poor；Flexible material is stretchable functional, but electric property extreme difference in general.
The preparation method of current stretchable conductive elastomer is to be mixed nanometer conductive material with elastomer, or will be led Material layer is attached to surface of elastomer.In drawing process, conducting material structure is changed significantly, and causes resistance to dramatically increase, and Elongation strain scope very little.Therefore, it is stretchable electricity to develop the conductive elastomer with high resistance stability, high elongation strain The research of sub- theory applied with device in the urgent need to.
The content of the invention
The present invention provides the Constructed wetlands and preparation method of a kind of multilayer conductive elastic composite.The composite is simultaneously With good tensility and electric conductivity, resistance variations are less than 2% in the case of simple tension 400%.
The structure of above-mentioned multilayer conductive elastic composite, it, which is constituted, includes dielectric layer and conductive layer, and preparation method is Conductive layer and dielectric replace laying composition in substrate.To ensure the mechanical strength and electric conductivity of composite, layer preferably Number is 50-500 layers.The number of plies very little, may cause the conductivity of composite material poor；The number of plies is too many, makes complicated and upper strata and leads Electric layer contracting property is deteriorated, and influences the uniformity of whole composite.
Multilayer conductive elastic composite structure schematic diagram of the present invention is shown in Figure of description 1, is dielectric with leading Electric layer alternating laying is formed；Preparation process refer to Figure of description 2, be said detail as per the embodiment in embodiment It is bright.
The dielectric layer is mixed by white oil with ultra-soft rubber with certain proportion, is sprayed after hot melt through aerial spraying pump Generation.The elastic layer made using the method has fabulous tensility energy, and highest drawing coefficient, up to more than 10 times, is mesh One of draw ratio most long material, is that multilayer conductive elastic composite realizes that ultra large deformation has established base in preceding quality of rubber materials Plinth, while being also the electrode layer of composite（CNT）There is provided attachment base bottom.
The conductive layer uses single armed CNT or multi-walled carbon nanotube, and CNT has excellent mechanics in itself Performance and light quality so that the elastic conduction composite has tough structure.
The multilayer conductive elastic composite uses " surface covering " method, and high-orientation carbon nanotube film is uniformly covered The elastic layer surface being pre-stretched in large deformation is covered, CNT is oriented parallel to elastic layer draw direction, forms lit-par-lit structure；Release The stepped construction is put, the elastomer of stretching of prestretching compresses carbon nano-tube film, forms multistage pleated structure, reference explanation book accompanying drawing Schematic diagram under 1 contraction state, along with the excellent mechanical property of CNT, with can stretch repeatedly, can distort repeatedly, can be anti- The characteristics of multiple bending is hardly damaged.
Current elastic electric conductor range of strain only has 30% or so, multilayer conductive elastic composite provided by the present invention Range of strain can reach 400%, and resistance rate of change in drawing process is less than 2%, and Reusability more than 2000 times, property It can decay still less than 5%, really realize ultra large deformation and the stable electrically conductive elastic composite of performance.
Brief description of the drawings
Fig. 1, the structural representation of multilayer conductive elastic composite,（1）For under extended state,（2）For under contraction state.
Fig. 2, the preparation process schematic diagram of multilayer conductive elastic composite.
Fig. 3, the same thickness difference number of plies places an order the composite material resistance of bit length and the relation of tensile elongation.
Fig. 4, the sample in cross section scanning electron microscope (SEM) photograph of identical number of plies different-thickness, the number of plies is 100 layers, wherein figure a, b, c, d couple The internal layer thickness answered is respectively 5 microns, 8 microns, 20 microns, 36 microns.
Fig. 5, resistance change curves figure during the bending of electrically conductive elastic composite, torsion, pressing, wherein figure a is bending In the case of resistance change curves, abscissa is bending diameter；It is resistance change curves in the case of rotation twist to scheme b, and abscissa is Unit centimetre number of turns；It is resistance change curves during pressing to scheme c, meets material strain amplitude when abscissa is pressing.
Fig. 6, stretches, bends after 1000 times repeatedly to electrically conductive elastic composite, again measurement bending, torsion, pressing During resistance change curves figure, wherein figure a for bending in the case of resistance change curves, abscissa is bending diameter；It is rotation to scheme b Turn resistance change curves under distorting event, abscissa is unit centimetre number of turns；Scheme c bent for resistance variations during pressing Line, meets material strain amplitude when abscissa is pressing.
The identical number of plies different-thickness resistance per unit length of Fig. 7, a and tensile elongation change curve；The identical numbers of plies of b are different Thickness resistance and tensile elongation change curve；C electrical conductivity and internal layer rubber thickness change curve.
Fig. 8, the sample object figure that embodiment finally gives.
Embodiment
Embodiments of the present invention are described in detail referring to Figure of description 2.
Multilayer conductive elastic composite of the present invention replaces laying in substrate by conductive layer and dielectric layer and constituted. Detailed step is as follows：
（1）The selection of substrate：It is limited to CNT elasticity and can not show a candle to rubber, if is used as base from the rubber of rebound performance difference Bottom, with the increase of laying carbon tube layer number, the conductive elastomer draw ratio of preparation will reduce.To solve this problem, it is ensured that Conductive elastomer draw ratio is basically unchanged, and we select the preferable hard rubber of rebound performance as sheet form base, substrate here Size：Long 50mm, wide 10mm.
（2）The preparation of conductive layer：By the substrate in step 1 according to required draw ratio to 1-5 times of original length, this implementation Example chooses maximum 5 times of multiple.Original aspect is respectively 50mm and 10mm, a length of 250mm after stretching, a width of 7mm.Then one is spread Layer CNT is as conductive layer, CNT a length of 85mm, a width of 6mm, and conductive elastomer is prepared needed for the several evidences of carbon tube layer The number of plies depending on.After laying is finished, a small amount of ethanol is dripped on the carbon nanotubes, is made CNT all infiltrations, be can reach carbon and receive The effect that mitron is brought into close contact with substrate.Described axial resistivity is all arranged parallel to substrate axial direction.Treat ethanol Substrate is retracted to reset condition after volatilization.
（3）It is dielectric to prepare：Treat that the substrate in step 2 is recovered to reset condition, then make in spraying rubber solutions above For dielectric, the rubber solutions are dissolved in organic solvent and obtained in certain proportion by ultra-soft flexible core, and the present embodiment is adopted Gained in hexamethylene is dissolved in ultra-soft flexible core, dissolving ratio is generally 1：15-1：30（Mass volume ratio）, adopt in the present embodiment With 1：23（g：ml）, its main function is to keep apart adjacent CNT, with the conductive elastomer of the number of plies needed for being made.Rubber The coating thickness of sol solution can manual control, can be by controlling spray time under the identical number of plies, the conductive bullet of thickness needed for being made Property body.100 layers, 5 microns, 8 microns, 20 microns, 36 microns four different internal layer thickness are selected in the present embodiment.Due to that can not keep away Exempt from error, coating thickness is too thin, and to be easily caused sample too thin, it is not easy to departs from from substrate；And spraying too thick can form larger pleat Wrinkle, upper strata carbon pipe fracture is easily caused in drawing process, the stability of conductive elastomer is influenceed, influences it to use scope.Spray Painting process is manually operable, also can mechanically spraying.
（4）According to the required number of plies, repeat step 2,3.
（5）After step 4 completion, sample is taken off from substrate, so that the multilayer conductive elastic composite stablized Material, reference explanation book accompanying drawing 8.
It is explained as follows for above implementation steps：
What the multilayer conductive elastic composite was made up of CNT and rubber, CNT herein can be single wall carbon Nanotube, can also be double-walled or multi-walled carbon nanotube, and number of plies numerical value is bigger, and electric conductivity is better.It refer to specification attached Under Fig. 3 same thickness difference number of plies, the resistance per unit length of composite and the relation of tensile elongation.
The multilayer conductive elastic composite of preparation, when being released to nature by extended state, carbon nanotube layer is in horizontal stroke To that can form cycle fold, the cycle fold ensure that the elastomer maintains the stabilization of resistance when significantly stretching is shunk.Please The sample in cross section scanning electron microscope (SEM) photograph of the identical number of plies different-thickness of refer to the attached drawing 4.
Above-mentioned steps（2）The laying method of the electrically conductive elastic composite carbon nanotube conducting layer is as follows：CNT Layer is prepared by a carbon nano pipe array, and the carbon nano pipe array needs orientations in the same direction substantially.First, according to institute Width is needed to choose multiple CNTs from carbon nano pipe array using the adhesive tape or blade of one fixed width and unanimously stretch outward, Drawn with certain speed along array carbon nanotube direction of growth stretching CNT, described multiple CNTs are actually perpendicular to Power effect lower edge draw direction progressively disengages the substrate of carbon nano pipe array, and in the presence of Van der Waals, makes selected Multiple CNTs join end to end with other adjacent CNTs respectively, pull straight, according to required length, prepare corresponding long Taking film frame and taking film for degree, removes after film, it is uniformly layed on substrate and dielectric parallel to substrate direction.
Step（3）The preparation method of middle different-thickness dielectric layer is as follows：Dielectric is by rubber solutions through aerial spraying pump Spraying is obtained, and spraying process need to keep spray gun perpendicular to substrate direction, and constant speed movement spray gun in left and right makes rubber solutions uniformly fall In substrate.Adjust air pump pressure and spray gun and substrate distance a to fixed value（Generally, pressure limit is about 30-40 psi, spray gun is about in 10-20cm, the present embodiment with substrate distance selects pressure to be 30psi, and distance is 15cm）, By controlling spray time, the dielectric layer of thickness needed for obtaining.
Step（5）The method that sample is departed from from substrate is as follows：Sample one end is set gently to depart from one from substrate Small segment distance, sample is gently drawn along this part obliquely, sample is departed from completely from substrate.This process is manually operable, and also may be used Mechanically actuated, and speed can not be too fast when drawing sample, must slowly carry out, and prevents from destroying sample.
Described multilayer conductive elastic composite, can keep the electric conductivity and mechanical performance of stabilization, in bending, turn round Turn, during pressing, still keep the stabilization of resistance value, resistance variations are no more than 0.5%（Referring to the drawings 5）.It is anti-by 1000 times After multiple stretching and bending, performance degradation is less than 1%（Referring to the drawings 6）.When internal layer rubber thickness is from when increasing to 36 microns for 5 microns, Under not pulled out condition, resistance per unit length increases to 41.7 Europe/cm from 31.7 Europe/cm；While stretchable maximum length It is held essentially constant, has only changed to 4.6 times from 5 times（Referring to the drawings 7a）.In addition the sample of different internal layer rubber thicknesses is being drawn Resistance variations are less than 1.5% during stretching（Referring to the drawings 7b）.Simultaneously with the reduction of internal layer thickness, electrical conductivity adds 29 times, 29S/m is increased from 1S/m（Referring to the drawings 7c）.Therefore, by controlling the thickness of internal layer rubber very easily to obtain institute Need the multilayer conductive elastic composite of electrical conductivity.
In addition, various equivalent modifications can also do other changes according to technical solution of the present invention, according to skill of the present invention The change that art scheme is done, all should be within the scope of the technical program be protected.

Claims (6)

1. a kind of multilayer conductive elastic composite, it is characterised in that：400% telescopic shape change is resistant to, range of strain is realized Resistance change rate is less than 2% in 400%；And durability is good, after repeated deformation 2000 times, performance degradation is less than 5%.
2. multilayer conductive elastic composite as claimed in claim 1, it is characterised in that including at least two parts：Electricity is situated between Matter layer, conductive layer；Building mode is that conductive layer and dielectric layer replace laying composition in substrate.
3. the dielectric layer as described in claim 2, it is characterised in that：It is dissolved in certain proportion by ultra-soft flexible core organic Obtained in solvent, ultra-soft flexible core material is rubber, preferably sebs, the preferred hexamethylene of organic solvent；Dissolving ratio preferably 1：15- 1：30（Mass volume ratio）；After stirring, formed using compression pump class spray gun spraying.
4. conductive layer as claimed in claim 2, it is characterised in that be made up of at least one layer of CNT, can be single wall carbon Nanotube, double-walled or multi-walled carbon nanotube, the CNT number of plies >=1, the number of plies are more, and electric conductivity is better；CNT axle To orientation all parallel to elastic layer axial direction.
5. dielectric layer as claimed in claim 3, it is characterised in that：Preparation method is spraying, can select hand spray, Can mechanical spray spray coating；The thickness degree, preferably 5 microns -50 microns of thickness are controlled according to spray time；Apply that thickness is too thin easily leads Cause sample too thin, it is not easy to depart from from substrate；And spray it is too thick can be formed compared with macrofold, be easily caused in drawing process The pipe fracture of layer carbon, influences the stability of conductive elastomer.
6. the preparation process of multilayer conductive elastic composite as claimed in claim 2 is as follows：
（1）The selection of substrate：CNT elasticity can not show a candle to rubber, if from rebound performance difference rubber as substrate, with The increase of laying carbon tube layer number, the conductive elastomer draw ratio of preparation will reduce；To solve this problem, it is ensured that conductive bullet Property body draw ratio be basically unchanged, the good hard rubber of present invention selection rebound performance is used as sheet form base；
（2）The preparation of conductive layer：By step（1）In substrate needed for draw ratio to long 1-5 times of original；Spread one layer of carbon Nanotube is as conductive layer, depending on the number of plies that conductive elastomer is prepared needed for the several evidences of carbon tube layer；Described axial resistivity All arranged parallel to substrate axial direction；After laying is finished, a small amount of ethanol is dripped on the carbon nanotubes, makes CNT whole Infiltration, can reach the effect that CNT is brought into close contact with substrate；Substrate is retracted to reset condition after ethanol volatilizees；
（3）It is dielectric to prepare：Treat step（2）In substrate recover to reset condition, then above spray rubber solutions conduct Dielectric, the rubber solutions are dissolved in organic solvent and obtained in certain proportion by ultra-soft flexible core, and its main function is Adjacent CNT is kept apart, with the electrically conductive elastic composite of the number of plies needed for being made；Spraying process is manually operable, Can mechanically spraying；By controlling spray time to control thickness；
（4）According to the required number of plies, repeat step（2）、（3）；
（5）Treat step（4）After completion, sample is taken off from substrate, so that the multilayer conductive elastic composite material stablized Material.
CN201610121247.8A 2016-03-04 2016-03-04 Multilayer conductive elastic composite Pending CN107154282A (en)

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CN201610121247.8A CN107154282A (en) 2016-03-04 2016-03-04 Multilayer conductive elastic composite

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110278702A (en) * 2019-06-04 2019-09-24 江南石墨烯研究院 A kind of high stretching high resiliency electromagnetic shielding composite material and preparation method thereof
CN113096853A (en) * 2021-04-12 2021-07-09 北京化工大学 Composite material based on two-dimensional nano conductive material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538088A (en) * 2014-12-30 2015-04-22 江南石墨烯研究院 Constructing and preparation scheme of conductive elastic composite material
CN104700945A (en) * 2015-02-10 2015-06-10 江南石墨烯研究院 Flexible pacemaker electrode wire capable of being stretched and twisted

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538088A (en) * 2014-12-30 2015-04-22 江南石墨烯研究院 Constructing and preparation scheme of conductive elastic composite material
CN104700945A (en) * 2015-02-10 2015-06-10 江南石墨烯研究院 Flexible pacemaker electrode wire capable of being stretched and twisted

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110278702A (en) * 2019-06-04 2019-09-24 江南石墨烯研究院 A kind of high stretching high resiliency electromagnetic shielding composite material and preparation method thereof
CN110278702B (en) * 2019-06-04 2021-02-19 江南石墨烯研究院 High-stretch high-elasticity electromagnetic shielding composite material and preparation method thereof
CN113096853A (en) * 2021-04-12 2021-07-09 北京化工大学 Composite material based on two-dimensional nano conductive material and preparation method thereof

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Application publication date: 20170912