CN109749121A - A kind of three-dimensional structure composite material and preparation method and purposes - Google Patents
A kind of three-dimensional structure composite material and preparation method and purposes Download PDFInfo
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Abstract
The present invention provides a kind of three-dimensional structure composite material and preparation method and purposes.Specifically disclose a kind of three-dimensional structure composite material, it is characterized in that, it successively coats nickel layer and layer gold by chemical plating method using polyurethane sponge as matrix and on polyurethane sponge surface and internal coated graphite alkene, and on graphene, encapsulates finally by dimethyl silicone polymer.This three-dimensional structure compound material flexible conductor has good tensility (stretchable maximum strain up to 30%), conductive stability (stretching, three kinds of deformation of bending and distortion) can be kept under different deformation, three-dimensional structure compound material flexible conductor of the invention solves the problems, such as fexible conductor elongation strain is not high, different deformation stability inferior is not high, long-time stability in use is bad, substantially increases electric conductivity.
Description
Technical field
The present invention relates to three-dimensional structure field of compound material more particularly to a kind of three-dimensional structure compound material flexible conductor and
Preparation method.
Background technique
In recent years, with the rapid development of flexible intelligent wearable electronic device, flexible conducting material is important as its
Backing material also has become a hot topic of research.Stretchable fexible conductor with satisfactory electrical conductivity and big strain stability inferior is in recent years
It is widely used in stretchable antenna, stretchable transistor, flexible super capacitor, electronic skin and touch in the research come
Screen, and fexible conductor will also play the role of in the development of the following intelligent device it is very important.
Therefore, in order to prepare high performance stretchable fexible conductor, people have carried out extensively its preparation method
Research, from the point of view of the research of recent report, it is one of simple directly and effective method is to utilize highly conductive nanometer material
Expect (such as graphene, carbon nanotube, carbon nano-fiber, metal nanometer line etc.) and the polymer material with good flexibility (as gathered
Dimethyl siloxane (PDMS), polyurethane (PU) etc.), nano material at the top of polymer material or is embedded in it by design
In, so that it may obtain the fexible conductor of this composite material.But this method have the defects that it is certain, for example, in order to
Keep a balance between the mechanical performance and electric conductivity of the fexible conductor arrived, the amount of the conductive filler of addition and polymer
Amount wants strict control, this also allows for requiring more harsh condition in preparation process.In addition, since this method prepares
Fexible conductor in conductive filler can be slid during applying external stress, therefore can be in the process of Reusability
In the problem of causing fexible conductor conductivity to decline and a series of unstable problem of performances.
To solve the above-mentioned problems, some other preparation methods has also been introduced under study for action to overcome above-mentioned lack in people
It falls into, for example, George M.Whitesides is proposed earliest introduces the period by pre-stretching-release process on elastomer
Property " corrugated " micro-structure can assign the good conductive stability of this fexible conductor and wider strainable range.But
This micro-structure preparation is relatively complicated in the process of transfer, is not suitable for large-scale industrial production.
Although above-mentioned technology all shows to make some progress in the research and application in terms of stretchable fexible conductor.
But there is higher tensility in face of how to prepare, while keeping the high-performance of conductive stability can under the deformation strained greatly
Fexible conductor is stretched, still there is very big challenge.
Summary of the invention
In view of this, the fexible conductor with three-dimensional conductive network structure is resistance to due to the preparation process of its low cost, machinery
Long property, conductive stability and the research hotspot for becoming fexible conductor preparation in recent years the advantages that can be mass-produced.Wherein, three
Tieing up graphene network structure becomes fexible conductor system because of its bigger serface, outstanding electric conductivity and good mechanical performance
Standby overriding concern material.
It is an object of the invention to overcome shortcoming and defect of the existing technology, the present invention is provided one kind and is led based on three-dimensional
The stretchable fexible conductor of electric network structure, the stretchable fexible conductor solve big conductive stability under straining and (are stretchable to
30% strain), conductive stability under different deformation (as stretched, bending and distortion transition) and Reusability stability (can be held
By lower 1000 circulation experiments of different deformation) and large-scale production the problem of.
The present invention is implemented with the following technical solutions:
In a first aspect, the present invention provides a kind of three-dimensional structure composite material, using polyurethane sponge as matrix and poly-
Urethane sponge surface and inside are coated with graphene, and successively coat nickel layer and layer gold by chemical plating on graphene, finally
It is encapsulated by dimethyl silicone polymer (PDMS).
In the technical solution of this case invention, polyurethane sponge pore size is 100~300 μm, and polyurethane sponge is thick
Degree is 0.5mm~2mm, preferably 0.8mm~1mm.
This case invention technical solution in, nickel layer thickness be 250~275nm, such as 250nm, 260nm, 265nm,
270nm, 275nm etc., preferably 260nm.
In the technical solution of this case invention, layer gold with a thickness of 315~350nm, such as 315nm, 320nm, 325nm,
330nm, 340nm, 345nm, 350nm etc., preferably 350nm.
In the inventive solutions, the three-dimensional structure composite material further includes electrode.
As the optimal technical scheme of composite material of the present invention, polyurethane sponge (the also referred to as polyurethane sponge
Layer) with a thickness of 0.5mm~2mm, preferably 0.8mm~1mm.
Preferably, the length of the polyurethane sponge is 15mm~30mm, preferably 20mm~25mm.
Preferably, the width of the polyurethane sponge is 5m~15mm, preferably 8mm~10mm.
Second aspect, the present invention provide the preparation method of three-dimensional structure composite material as described in relation to the first aspect, the side
Method the following steps are included:
(1) polyurethane sponge is placed in the solution of graphene oxide and is impregnated, then will be soaked with oxidation with hot hydroiodic acid
The polyurethane sponge of graphene is restored, and is dipped to fully reacting repeatedly, is baked to, and graphene sponge is obtained；
(2) graphene sponge is put into chemical nickel-plating solution after activated solution impregnates, makes graphene sponge
By one layer of nickel coated, then the golden slot of displacement will be put by the graphene sponge of nickel coated, subtract nickel layer thickness by replacing reaction
It is small, coat sample by layer gold；
(3) it will be put into the golden slot of reduction after above-mentioned sample wash, so that layer gold is thickend by the method for chemical plating；
(4) by step (3) sample wash it is dry after, add electrode, and by priming by vacuum PDMS, then solidify,
Three-dimensional structure compound material flexible conductor is made.
Step (1) of the present invention prepares the polyurethane sponge of graphene coated, so that an insulator polyurethane sponge becomes
Conductive three-dimensional structure, obtains the graphene sponge with satisfactory electrical conductivity, to provide good material for subsequent chemistry plating
Material.
Method of the invention is obtained by impregnating absorption for several times and restoring by graphene using polyurethane sponge as base material
The graphene sponge of cladding deposits gold-nickel composite material layer on graphene sponge surface, finally then by chemical plating method
It is packaged by priming by vacuum PDMS, obtains three-dimensional structure compound material flexible conductor of good performance, this method solution
The problem for fexible conductor preparation process complexity of having determined, while obtained stretchable fexible conductor has biggish tensility, good
Good cyclical stability and the features such as being produced on a large scale.
As the optimal technical scheme of the method for the invention, the method also includes step is carried out before step (1)
(1) ': polyurethane sponge being cleaned with deionized water and dehydrated alcohol, is then dried.
As the optimal technical scheme of the method for the invention, step (1) the polyurethane sea for preparing graphene coated
Continuous method the following steps are included:
(A) it impregnates: polyurethane sponge being placed in the solution of graphene oxide and is impregnated；
(B) it restores: the polyurethane sponge for being soaked with graphene oxide being restored with the hydroiodic acid of heat；
(C) dry, obtain the polyurethane sponge of graphene coated.
Preferably, the concentration of the solution of step (A) described graphene oxide be 1g/L~8g/L, such as 1g/L, 1.5g/L,
2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L, 7g/L, 7.5g/L or 8g/L
Deng preferably 3g/L~5g/L.
Preferably, the time of step (A) described immersion is 2h~6h, preferably 3h~5h.
Preferably, the time of step (B) described reduction is 10min~20min, preferably 10min~15min.
Preferably, the concentration calibration of step (B) described hydroiodic acid are as follows: make to go in the solution of hydroiodic acid and graphene oxide
The volume ratio of ionized water is 1:1~5, preferably 1:1~2.
Preferably, the temperature of step (B) described hydroiodic acid be 50 DEG C~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C,
70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., preferably 80 DEG C.
Preferably, step (B) reduction carries out under water bath condition, and bath temperature is 80 DEG C~90 DEG C, preferably 85 DEG C
~90 DEG C.
As the optimal technical scheme of the method for the invention, step (1) prepares the polyurethane sponge of graphene coated
In the process, further include the steps that being washed before step (C) is dry after step (B) is restored.
It preferably, further include dry in step (C) during step (1) prepares the polyurethane sponge of graphene coated
Later, the step of being repeated in step (A)-(C), duplicate number is preferably 1 time~7 times, such as preferably 1 time, 2 times, 3 times, 4
Secondary, 5 times, 6 times or 7 times, preferably 3 times~5 times, further preferred 4 times or 5 times.
It preferably, further include repeating last time during step (1) prepares the polyurethane sponge of graphene coated
Reduction step after the operation of deionized water cleaning at least once is carried out before drying steps.
As the optimal technical scheme of the method for the invention, step (2) the activated solution group becomes PdSO4And H2SO4
Mixed solution.
Preferably, PdSO in the activated solution4Concentration be 5~30ppm, such as 5ppm, 10ppm, 15ppm, 20ppm,
25ppm, 30ppm etc., preferably 20ppm.
Preferably, H in the activated solution2SO4Concentration be 5~20mol/L, such as 5mol/L, 12mol/L, 15mol/L,
18mol/L, 20mol/L etc., preferably 13mol/L.
As the optimal technical scheme of the method for the invention, step (2) the chemical nickel-plating solution group becomes NiSO4·
6H2O, NaH2PO2(sodium hypophosphite) and Na3C6H5O7·2H2The mixed solution of O (Sodium Citrate, usp, Dihydrate Powder).
Preferably, NiSO in the chemical nickel-plating solution4·6H2O concentration is 5~30g/L, such as 5g/L, 10g/L, 15g/
L, 20g/L, 25g/L, 30g/L etc., preferably 25g/L.
Preferably, NaH in the chemical nickel-plating solution2PO2Concentration be 10~50g/L, such as 10g/L, 15g/L, 20g/L,
25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L etc., preferably 30g/L.
Preferably, Na in the chemical nickel-plating solution3C6H5O7·2H2O concentration be 1~15g/L, such as 1g/L, 3g/L,
5g/L, 7g/L, 9g/L, 12g/L, 15g/L etc., preferably 10g/L.
Preferably, the chemical nickel-plating solution pH is 1~7, such as 1,2,3,4,5,6,7 etc., preferably 4.5.
Preferably, the chemical nickel-plating solution temperature be 50~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C,
75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C etc., preferably 85 DEG C.
Preferably, the chemical nickel plating time be 1-10min, such as 1min, 2min, 3min, 4min, 5min, 6min,
7min, 8min, 9min, 10min etc., preferably 5min.
Preferably, in the chemical nickel plating nickel layer thickness be 250~275nm, such as 250nm, 260nm, 265nm,
270nm, 275nm etc., preferably 260nm.
As the optimal technical scheme of the method for the invention, in the golden slot solution of step (2) displacement, solution composition is
Na3Au(SO3)2(gold sodium sulfide), Na2SO3(sodium sulfite) and N (CH2PO3H2)3The mixing of (amino trimethyl phosphonic acids) is molten
Liquid.
Preferably, Na in the golden slot solution of the displacement3Au(SO3)2Concentration be 1~10g/L, such as 1g/L, 2g/L, 3g/L,
4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L etc., preferably 3g/L.
Preferably, Na in the golden slot solution of the displacement2SO3Concentration be 10~50g/L, such as 10g/L, 15g/L, 20g/L,
25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L etc., preferably 35g/L.
Preferably, N (CH in the golden slot solution of the displacement2PO3H2)3Concentration be 10~50g/L, such as 10g/L, 15g/L,
20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L etc., preferably 20g/L.
Preferably, the golden slot pH value of solution of the displacement is 1~7, such as 1,2,3,4,5,6,7 etc., preferably 7.
Preferably, the displacement gold solution temperature is 50~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75
DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C etc., preferably 80 DEG C.
Preferably, the displacement golden reaction time is 1-30min, for example, 1min, 5min, 10min, 15min, 20min,
25min, 30min etc., preferably 20min.
As the optimal technical scheme of the method for the invention, in the golden slot solution of step (3) reduction, solution composition is
Na3Au(SO3)2(gold sodium sulfide), Na2SO3(sodium sulfite), Na3C6H5O7·2H2O (trisodium citrate dihydrate) and CH4N2S
The mixed solution of (thiocarbamide).
Preferably, Na in the golden slot solution of the reduction3Au(SO3)2Concentration be 1~10g/L, such as 1g/L, 2g/L, 3g/L,
4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L etc., preferably 2g/L.
Preferably, Na in the golden slot solution of the reduction2SO3Concentration be 10~50g/L, such as 10g/L, 15g/L, 20g/L,
25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L etc., preferably 20g/L.
Preferably, Na in the golden slot solution of the reduction3C6H5O7·2H2O concentration be 1~20g/L, such as 1g/L, 5g/L,
10g/L, 15g/L, 20g/L etc., preferably 10g/L.
Preferably, CH in the golden slot solution of the reduction4N2S concentration is 0.1~2g/L, such as 0.1g/L, 0.3g/L, 0.5g/
L, 0.8g/L, 1.0g/L, 1.2g/L, 1.5g/L, 1.8g/L, 2.0g/L etc., preferably 1g/L.
Preferably, the golden slot pH value of solution of the reduction is 1~7, such as 1,2,3,4,5,6,7 etc., preferably 7.
Preferably, the reduction gold solution temperature is 20~80 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45
DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C etc., preferably 50 DEG C.
Preferably, the reduction golden reaction time is 5-50min, for example, 5min, 10min, 15min, 20min, 25min,
30min, 35min, 40min, 45min, 50min etc., preferably 30min.
Preferably, after the reaction of reduction gold, in composite material layer gold with a thickness of 315~350nm, such as 315nm,
320nm, 325nm, 330nm, 340nm, 345nm, 350nm etc., preferably 350nm.And nickel layer with a thickness of 250~275nm, such as
250nm, 260nm, 265nm, 270nm, 275nm etc., preferably 260nm.
As the optimal technical scheme of the method for the invention, step (4) the priming by vacuum PDMS and cure package
Process is after electrode has been pasted with conductive silver paste in obtained composite material both ends, to be placed in reeded polytetrafluoroethylene (PTFE)
In mold, by the way that configured PDMS (ratio of dimethyl siloxane and curing agent is 10:1) is poured on the composite,
And place it in baking oven and vacuumize, it takes out, finally solidifies in high temperature oven to get stretchable flexibility is arrived after placing 30min
Conductor.
In this optimal technical scheme, first material is packaged by the way of PDMS is perfused under vacuum, is then carried out again
Solidification, making fexible conductor not only has good encapsulation, also has good tensility and cyclical stability, stretchable to answer
Become up to 30%.
Preferably, the mass ratio of step (4) dimethylsilane and curing agent be 20~5:1, such as 20:1,18:1,
15:1,12:1,10:1,8:1 or 5:1 etc., preferably 10:1.
Preferably, in step (4) described vacuum drying oven standing time be 5~40min, such as 5min, 10min, 15min,
20min, 25min, 30min, 35min, 40min etc., preferably 30min.
Preferably, step (4) solidification temperature be 60 DEG C~90 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C,
85 DEG C, 90 DEG C etc., preferably 70 DEG C.
Preferably, step (4) curing time be 1~5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h,
4.5h, 5h etc., preferably 3h.
Third aspect of the present invention provides purposes of the three-dimensional structure composite material of the present invention as fexible conductor.
Compared with the prior art, the invention has the following beneficial effects:
(1) present invention is first prepared on the polyurethane sponge with three-dimensional framework material by absorbing and reducing method repeatedly
Then graphene sponge with good conductivity deposits gold-nickel by the method for chemical plating on graphene sponge, obtain by gold-
Nickel-graphite alkene coats the composite material that polyurethane sponge is formed, and is packaged simultaneously using PDMS is perfused under vacuum environment to it
Further three-dimensional structure compound material flexible conductor is obtained after solidification.This three-dimensional structure compound material flexible conductor has good
Tensility (stretchable maximum strain up to 30%), conductive stability can be kept (to stretch, bending and turn round under different deformation
Bent three kinds of deformation), it is not high, different in elongation strain that three-dimensional structure compound material flexible conductor of the invention solves fexible conductor
The problem that deformation stability inferior is not high, long-time stability in use is bad, substantially increases electric conductivity.
(2) preparation method of the invention is simple, reduces costs from raw material, which solves fexible conductor work
Skill is complicated, at high cost, and the fexible conductor electric conductivity prepared is low and the poor problem of recycling, this preparation method
It is applicable to be mass produced.
(3) method that the present invention uses chemical plating, compared to electro-plating method, obtained metal layer more evenly, is enabled to
Good electric conductivity is also kept in the case where deformation.
Detailed description of the invention
Fig. 1 is that the surface layer gold SEM of three-dimensional structure compound material flexible conductor schemes；
Fig. 2 is that the skeleton SEM of three-dimensional structure compound material flexible conductor schemes；
Fig. 3 is the XRD diagram of the composite material of nickel coated in three-dimensional structure compound material flexible conductor and preparation process.
Fig. 4 is the composite material of nickel coated in three-dimensional structure compound material flexible conductor and preparation process by same
Relative resistance change figure during the extension test of the material that packaged type obtains respectively.
Fig. 5 three-dimensional structure compound material flexible conductor boundary mapping figure, illustrates the thickness of layer gold and nickel layer.
Fig. 6 three-dimensional structure compound material flexible conductor is by relative resistance change in repeatedly bending and torsion test process
Figure.
Specific embodiment
The Applicant declares that the present invention is explained by the above embodiments detailed construction and technique of the invention, but the present invention
It is not limited to above-mentioned detailed construction and technique, that is, does not mean that the present invention must rely on above-mentioned detailed construction and technique could be real
It applies.Person of ordinary skill in the field should be understood that any improvement in the present invention, to the equivalent of each raw material of product of the present invention
Replacement and addition, the selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.It is real
It applies example 1 and prepares three-dimensional structure Au-Ni compound material flexible conductor
(1) after cleaning polyurethane sponge layer deionized water and dehydrated alcohol repeatedly, it is put into baking oven drying, is placed it in
3h is impregnated in the solution of the graphene oxide of 3g/L, and then the polyurethane sponge for being soaked with graphene oxide is existed with 80 DEG C of hydroiodic acids
Reduction 10min is carried out under 85 DEG C of water bath conditions, and is washed, repeatedly after soaking and reducing 3 times, deionized water is cleaned at least once, so
Graphene sponge is dried in an oven afterwards, obtains the graphene sponge with satisfactory electrical conductivity；
(2) by the graphene sponge with good conductivity by including 20ppm PdSO4With 13mol/L H2SO4Solution
Activated solution impregnate after, be put into comprising 25g/L NiSO4·6H2O, 30g/L NaH2PO2(sodium hypophosphite) and 10g/L
Na3C6H5O7·2H2In the solution of 4.5 chemical nickel platings of the pH value of O, at 85 DEG C, chemical nickel plating 5min makes graphene sponge quilt
Then the nickel coated of a thin layer of 260nm thickness will be put into the golden slot of displacement by the graphene sponge of nickel coated, replace golden slot solution
In, solution composition is 3g/L Na3Au(SO3)2(gold sodium sulfide), 35g/L Na2SO3(sodium sulfite), 20g/L N
(CH2PO3H2)3(amino trimethyl phosphonic acids), pH value of solution 7.Displacement reaction carries out at 80 DEG C, reacts 20 minutes.Pass through displacement
Reaction reduces nickel layer thickness, coats sample by layer gold；
(3) above-mentioned sample is put into after deionized water is rinsed and is put into the golden slot of reduction, restoring golden slot solution composition is 2g/
L Na3Au(SO3)2(gold sodium sulfide), 20g/L Na2SO3(sodium sulfite), 10g/L Na3C6H5O7·2H2O (two hydration lemons
Lemon acid sodium), 1g/L CH4N2S (thiocarbamide), pH value of solution 7.Reduction reaction temperature is 50 DEG C, reacts 30min, passes through chemical plating
Method makes layer gold thicken, and layer gold is with a thickness of 350nm；
(4) with the composite material both ends conductive silver that after the drying of deionized water repeated flushing, will be obtained after sample being taken out
It after slurry has pasted electrode, is placed in in reeded Teflon mould, by by configured PDMS (dimethyl silica
The ratio of alkane and curing agent is 10:1) it pours under vacuum on the composite, and place it in baking oven and vacuumize, it places
It is taken out after 30min, solidifies 3h in 70 DEG C of high temperature ovens finally to get stretchable fexible conductor is arrived.
Embodiment 2 prepares three-dimensional structure Au-Ni compound material flexible conductor
(1) after cleaning polyurethane sponge layer deionized water and dehydrated alcohol repeatedly, it is put into baking oven drying, is placed it in
5h is impregnated in the solution of the graphene oxide of 5g/L, and then the polyurethane sponge for being soaked with graphene oxide is existed with 80 DEG C of hydroiodic acids
Reduction 5min is carried out under 90 DEG C of water bath conditions, and is washed, repeatedly after soaking and reducing 5 times, at least once, then deionized water is cleaned
Graphene sponge is dried in an oven, obtains the graphene sponge with satisfactory electrical conductivity；
(2) by the graphene sponge with good conductivity by including 20ppm PdSO4With 13mol/L H2SO4Solution
Activated solution impregnate after, be put into comprising 25g/L NiSO4·6H2O, 30g/L NaH2PO2(sodium hypophosphite) and 10g/L
Na3C6H5O7·2H2In the solution of 4.5 chemical nickel platings of the pH value of O, at 85 DEG C, chemical nickel plating 5min makes graphene sponge quilt
Then the nickel coated of a thin layer of 260nm thickness will be put into the golden slot of displacement by the graphene sponge of nickel coated, replace golden slot solution
In, solution composition is 3g/L Na3Au(SO3)2(gold sodium sulfide), 35g/L Na2SO3(sodium sulfite), 20g/L N
(CH2PO3H2)3(amino trimethyl phosphonic acids), pH value of solution 7.Displacement reaction carries out at 80 DEG C, reacts 20 minutes.Pass through displacement
Reaction reduces nickel layer thickness, coats sample by layer gold；
(3) above-mentioned sample is put into after deionized water is rinsed and is put into the golden slot of reduction, restoring golden slot solution composition is 2g/
L Na3Au(SO3)2(gold sodium sulfide), 20g/L Na2SO3(sodium sulfite), 10g/L Na3C6H5O7·2H2O (two hydration lemons
Lemon acid sodium), 1g/L CH4N2S (thiocarbamide), pH value of solution 7.Reduction reaction temperature is 50 DEG C, reacts 30min, passes through chemical plating
Method makes layer gold thicken, and layer gold is with a thickness of 350nm；
(4) with the composite material both ends conductive silver that after the drying of deionized water repeated flushing, will be obtained after sample being taken out
It after slurry has pasted electrode, is placed in in reeded Teflon mould, by by configured PDMS (dimethyl silica
The ratio of alkane and curing agent is 10:1) it pours under vacuum on the composite, and place it in baking oven and vacuumize, it places
It is taken out after 30min, solidifies 3h in 70 DEG C of high temperature ovens finally to get stretchable fexible conductor is arrived.
Embodiment 3 prepares three-dimensional structure Ni material flexibility conductor
(1) after cleaning polyurethane sponge layer deionized water and dehydrated alcohol repeatedly, it is put into baking oven drying, is placed it in
5h is impregnated in the solution of the graphene oxide of 5g/L, and then the polyurethane sponge for being soaked with graphene oxide is existed with 80 DEG C of hydroiodic acids
Reduction 5min is carried out under 90 DEG C of water bath conditions, and is washed, repeatedly after soaking and reducing 5 times, at least once, then deionized water is cleaned
Graphene sponge is dried in an oven, obtains the graphene sponge with satisfactory electrical conductivity；
(2) by the graphene sponge with good conductivity by including 20ppm PdSO4With 13mol/L H2SO4Solution
Activated solution impregnate after, be put into comprising 25g/L NiSO4·6H2O, 30g/L NaH2PO2(sodium hypophosphite) and 10g/L
Na3C6H5O7·2H2In the solution of 4.5 chemical nickel platings of the pH value of O, at 85 DEG C, chemical nickel plating 5min makes graphene sponge quilt
The nickel coated of a thin layer of 260nm thickness；
(3) with the composite material both ends conductive silver that after the drying of deionized water repeated flushing, will be obtained after sample being taken out
It after slurry has pasted electrode, is placed in in reeded Teflon mould, by by configured PDMS (dimethyl silica
The ratio of alkane and curing agent is 10:1) it pours under vacuum on the composite, and place it in baking oven and vacuumize, it places
It is taken out after 30min, solidifies 3h in 70 DEG C of high temperature ovens finally to get stretchable fexible conductor is arrived.
Embodiment 4 is detected by X-ray diffraction
By X-ray diffraction method in three-dimensional structure compound material flexible conductor and preparation process nickel coated it is compound
Material is detected, and testing result is shown in Fig. 3, be can be seen that according to XRD result and has been coated with by means of the present invention in nickel surface
Layer gold.
Relative resistance change during 5 extension test of embodiment
By relative resistance change during the result progress extension test to embodiment 1 and embodiment 3, experimental method is
Stretch processing is carried out to test sample, while test resistance changes, resistive when detecting elongation strain 0-30, under different conditions
Can, referring to fig. 4, only the sample resistance variation with nickel layer is obvious known to experimental result, and the sample with layer gold for experimental result
Resistance stabilization.
The variation of relative resistance during the bending of embodiment 6 and distortion
By relative resistance change during the result progress extension test to embodiment 1 and embodiment 3, experimental method is
Bending and distortion processing are carried out to test sample, while testing resistance variations for the first time and at the 1000th time, experimental result referring to
Fig. 6, resistance variations known to experimental result are nearly free from variation with the increase of bending and distortion test.
Claims (9)
1. a kind of three-dimensional structure composite material, which is characterized in that it is using polyurethane sponge as matrix and on polyurethane sponge surface
With internal coated graphite alkene, and nickel layer and layer gold are successively coated by chemical plating method on graphene, finally by poly- diformazan
Radical siloxane (PDMS) encapsulates；
Preferably, polyurethane sponge pore size is 100~300 μm, and polyurethane sponge is with a thickness of 0.5mm~2mm, preferably
0.8mm~1mm；
Preferably, nickel layer thickness is 250~275nm；
Preferably, layer gold with a thickness of 315~350nm.
2. the preparation method of three-dimensional structure composite material according to claim 1, which comprises the steps of:
(1) polyurethane sponge is placed in the solution of graphene oxide and is impregnated, then will be soaked with graphite oxide with hot hydroiodic acid
The polyurethane sponge of alkene is restored, and is dipped to fully reacting repeatedly, is baked to, and graphene sponge is obtained；
(2) graphene sponge is put into chemical nickel-plating solution after activated solution impregnates, makes graphene sponge by one
Then layer nickel coated will be put into the golden slot of displacement by the graphene sponge of nickel coated, reduce nickel layer thickness by replacing reaction, make
Sample is coated by layer gold；
(3) it will be put into the golden slot of reduction after above-mentioned sample wash, so that layer gold is thickend by the method for chemical plating；
(4) by step (3) sample wash it is dry after, add electrode, and by priming by vacuum PDMS, then solidify, be made
Three-dimensional structure compound material flexible conductor.
3. the preparation method of three-dimensional structure composite material according to claim 2, which is characterized in that step (1) described system
The method of the polyurethane sponge of standby graphene coated the following steps are included:
(A) it impregnates: polyurethane sponge being placed in the solution of graphene oxide and is impregnated；
(B) it restores: the polyurethane sponge for being soaked with graphene oxide being restored with the hydroiodic acid of heat；
(C) dry, obtain the polyurethane sponge of graphene coated.
4. the preparation method of three-dimensional structure composite material described in a kind of claim 2, which is characterized in that step (2) described activation
Solution composition is PdSO4And H2SO4Mixed solution；
Preferably, PdSO in activated solution4Concentration is 5~30ppm；
Preferably, H in activated solution2SO4Concentration is 5~20mol/L.
5. the preparation method of three-dimensional structure composite material described in a kind of claim 2, which is characterized in that chemical plating in step (2)
Nickel solution group becomes NiSO4·6H2O、NaH2PO2And Na3C6H5O7·2H2The mixed solution of O；
Preferably, NiSO in chemical nickel-plating solution4·6H2O concentration is 5~30g/L；
Preferably, NaH in the chemical nickel-plating solution2PO2Concentration is 10~50g/L；
Preferably, Na in the chemical nickel-plating solution3C6H5O7·2H2O concentration is 1~15g/L,.
Preferably, the chemical nickel-plating solution pH is 1~7.
Preferably, the chemical nickel-plating solution temperature is 50~100 DEG C.
6. the preparation method according to claim 4, which is characterized in that replacing golden slot solution composition described in step (2) is
Na3Au(SO3)2、Na2SO3With N (CH2PO3H2)3Mixed solution；
Preferably, Na in the golden slot solution of the displacement3Au(SO3)2Concentration is 1~10g/L；
Preferably, Na in the golden slot solution of the displacement2SO3Concentration is 10~50g/L；
Preferably, N (CH in the golden slot solution of the displacement2PO3H2)3Concentration is 10~50g/L；
Preferably, the golden slot pH value of solution of the displacement is 1~7；
Preferably, the displacement gold solution temperature is 50~100 DEG C.
7. the preparation method according to claim 4, which is characterized in that in the golden slot solution of step (3) reduction, solution group
As Na3Au(SO3)2, Na2SO3, Na3C6H5O7·2H2O and CH4N2The mixed solution of S；
Preferably, Na in the golden slot solution of the reduction3Au(SO3)2Concentration is 1~10g/L；
Preferably, Na in the golden slot solution of the reduction2SO3Concentration is 10~50g/L；
Preferably, Na in the golden slot solution of the reduction3C6H5O7·2H2O concentration is 1~20g/L；
Preferably, CH in the golden slot solution of the reduction4N2S concentration is 0.1~2g/L；
Preferably, the golden slot pH value of solution of the reduction is 1~7；
Preferably, the reduction gold solution temperature is 20~80 DEG C.
8. the preparation method according to claim 4, which is characterized in that step (4) the priming by vacuum PDMS process is to incite somebody to action
After obtained composite material both ends post electrode, by pouring configured PDMS, vacuumize process is solid in high temperature
Change to get composite material is arrived；
Preferably, the configured PDMS is the composition of dimethyl siloxane and curing agent, dimethyl-silicon more preferably
Oxygen alkane and curing agent ratio are 5-15:1.
9. purposes of the three-dimensional structure composite material described in claim 1 as fexible conductor.
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