CN109336089A - The CNTs composite material and preparation method and application of a kind of nanometer of modified by silver - Google Patents
The CNTs composite material and preparation method and application of a kind of nanometer of modified by silver Download PDFInfo
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- CN109336089A CN109336089A CN201811054749.9A CN201811054749A CN109336089A CN 109336089 A CN109336089 A CN 109336089A CN 201811054749 A CN201811054749 A CN 201811054749A CN 109336089 A CN109336089 A CN 109336089A
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to conducing composite material technical fields, disclose the CNTs composite material and preparation method and application of a kind of nanometer of modified by silver.Carbon nanotube is successively used P-TES carry out UV-induced grafting and N-TES self-assembling reaction, obtains the carbon nanotube of surface molecular graft modification；Then it is added in reducing agent solution that ultrasonic mixing is uniform after being sensitized, obtains mixed liquor, then gained mixed liquor is added to ultrasonic mixing in silver ammino solution and is reacted, product is separated, washed, dried, and obtains the CNTs composite material of nanometer modified by silver.Carbon nano tube surface is successfully grafted and has gone up TES molecule by the method for the present invention, formed it is stable be connected chemically, boundary strength will be far superior to physisorption；And nano silver is uniformly distributed, and particle is tiny, can be effectively improved interfacial wettability；Gained composite material has excellent antibacterial and electric conductivity, can be applied to the preparation of antibacterial and conductive coating in flexible electronic device.
Description
Technical field
The invention belongs to conducing composite material technical fields, and in particular to the CNTs composite material of a kind of nanometer of modified by silver and
Preparation method and application.
Background technique
In recent years, the demand of portable intelligent device increases rapidly.Flexible, stretchable electronic equipment, including electronics skin
Skin, flexible display, wearable computer equipment, flexible solar panel etc., have gone under the spotlight in epoch.But now
Until, most of research all concentrates on the noble metals such as exploitation silver, gold.Wherein for economy, silver-colored use is wider
It is general, although it is also all highest in all metals that fine silver, which has good ductility, electric conductivity and thermal conductivity,.But flexible apparatus
Preferable mechanical property must also be kept under severe conditions, such as is stretched, bending.Therefore, there is an urgent need to study composite material
Guarantee to improve mechanical property while electric conductivity.
Carbon nanotube (CNTs) has good mechanical property, and it is 100 times of steel that tensile strength, which reaches 50-200GPa, close
Degree but only has the 1/6 of steel.Its elasticity modulus is suitable with the elasticity modulus of diamond up to 1TPa, about 5 times of steel.Simultaneously
Carbon nanotube also has good conductive property and good heat transfer property.If being matrix and carbon nanotube by Other Engineering material
Composite material is made, composite material exhibits can be made to go out good intensity, elasticity, fatigue resistance and isotropism, gives composite material
Performance bring great improvement.If electrode and connection line to prepare flexible apparatus etc. can show excellent mechanics
Performance and thermal stability.
One of an important factor for state of interface of composite material is influence composite property.Between CNTs and Ag matrix
Boundary moisture has to be optimized, that is to say, that excellent properties of the CNTs in composite membrane can reach further by interface modification
Performance, but physisorption generates between Ag and CNTs bond strength is weaker and be connected chemically relatively strong.So CNTs points
Sub- modification and the research of nanometer modified by silver have great importance.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of nanometer
The preparation method of the CNTs composite material of modified by silver.
It is multiple that another object of the present invention is to provide a kind of CNTs of nanometer modified by silver being prepared by the above method
Condensation material.
A further object of the present invention is to provide the CNTs composite materials of above-mentioned nanometer modified by silver in flexible electronic device
Application.
Another object of the present invention is to provide application among the above.
The object of the invention is achieved through the following technical solutions:
The preparation method of the CNTs composite material of a kind of nanometer of modified by silver, including following preparation step:
(1) carbon nanotube P-TES photo-grafting:
CNTs is added to P-TES, and (6- (3- triethoxysilylpropyltetrasulfide amino) -1,3,5- triazine -2,4- is two-fold
Nitrogen) ultrasonic disperse reaction, solid product are separated, are dried in alcoholic solution, photo-grafting is then carried out under ultraviolet irradiation condition
Reaction, obtains the carbon nanotube (CNTs-PTES) of P-TES photo-grafting；
(2) N-TES self assembly:
By step (1) prepare CNTs-PTES be added to N-TES (6- (3- triethoxysilylpropyltetrasulfide amino) -1,
3,5- triazine -2,4-, bis- sodium mercaptides) be stirred to react in aqueous solution, by after reaction mixed liquor cleaning, be evaporated to get to surface point
The carbon nanotube (CNTs-P&NTES) of sub- graft modification；
(3) nanometer modified by silver:
CNTs-P&NTES obtained by step (2) is added in sensitizing solution and carries out sensitized reaction, then by the product after sensitization
It is uniform to be added to ultrasonic mixing in reducing agent solution, obtains mixed liquor, then gained mixed liquor is added to ultrasound in silver ammino solution
Hybrid reaction, product are separated, washed, dried, and obtain the CNTs composite material (CNTs AgNP) of nanometer modified by silver.
Preferably, it is 2~10g/L, the P- that CNTs described in step (1), which is added to the concentration in P-TES alcoholic solution,
The concentration of P-TES is 0.5~0.8g/L in TES alcoholic solution.
Preferably, the time of the reaction of ultrasonic disperse described in step (1) is 10~30min.
Preferably, solid product described in step (1) separated, dry refer to it is dry in 100 DEG C of vacuum after vacuum filtration
Dry 4~the 8h of dry case.
Preferably, ultraviolet irradiation condition described in step (1) are as follows: a length of 256~365nm of ultraviolet light wave, intensity of illumination are
0.1~2J/cm2, light application time is 300~700s.
Preferably, the concentration of N-TES aqueous solution described in step (2) is 0.5~3g/L.
Preferably, it is stirred to react described in step (2) and refers to that stirring at normal temperature reacts 40~80min.
Preferably, sensitizing solution described in step (3) refers to containing 10~30g/L SnCl2It is water-soluble with 2~8g/L hydrochloric acid
Liquid.
Preferably, reducing agent solution described in step (3) refers to containing 20~50g/L glucose, 20~50g/L tartaric acid
With the aqueous solution of 50~100ml/L ethyl alcohol.
Preferably, the temperature of the reaction of ultrasonic mixing described in step (3) is 25 DEG C, and the time is 1~2h, is used after the reaction was completed
Ice-water bath, which handles 30~60min, prevents overreaction.
The CNTs composite material of a kind of nanometer of modified by silver, is prepared by the above method.
Application of the CNTs composite material of above-mentioned nanometer modified by silver in flexible electronic device.
The principle of the present invention are as follows: Combined Treatment method is used, ultraviolet light irradiation grafting and numerator self-assembly technique are combined,
Homemade P-TES molecule is grafted to CNTs using the irradiation of ultraviolet light, forms stable covalent linkage, recycles self-control
N-TES and P-TES hydrolytic condensation complete self assembly, finally make CNTs Thiolation.Using S and N to the good adsorbent of silver ion
The pre- silver-plated process in the surface CNTs is obtained into the CNTs nanocomposite of nanometer modified by silver with the method for chemical plating.In the present invention
Molecule grafting after it is silver-plated be substantially better than physisorption, the composite material of preparation has excellent electric conductivity, Neng Gouying
For flexible manufacturing field.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) carbon nano tube surface is successfully grafted and has gone up TES molecule by the method for the present invention, formed it is stable be connected chemically, boundary
Surface intensity will be far superior to physisorption；And nano silver is uniformly distributed, and particle is tiny (about 5nm), can be effectively improved boundary
Face wetability；
(2) composite material prepared by the present invention combines the advantages of nano silver and CNTs, has excellent antibacterial and conduction
Performance can be applied to the preparation of antibacterial and conductive coating in flexible electronic device.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of CNTs-P&NTES and corresponding surface molecular graft modification front and back carbon nanometer in embodiment 1
Transmission electron microscope (TEM) figure of pipe；
Fig. 2 is surface shape of the gained CNTs@AgNP at different amplification ((a)~(c)) after modified by silver in embodiment 1
Looks TEM figure；
The XPS that Fig. 3 is 1 gained CNTs-P&NTES of embodiment schemes；
Fig. 4 is the XPS swarming fitting result figure of 1 gained CNTs-P&NTES of embodiment；
Fig. 5 is the infrared spectrum comparison diagram of original CNTs and gained CNTs-P&NTES in embodiment 1.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Raw materials used P-TES (6- (3- triethoxysilylpropyltetrasulfide amino) -1,3,5- triazine-in following embodiment
The two-fold nitrogen of 2,4-) and N-TES (two sodium mercaptides of 6- (3- triethoxysilylpropyltetrasulfide amino) -1,3,5- triazine -2,4-) is
For current material (Kang Z X, Mori K, Oishi Y.Surface modification of magnesium alloys
using triazine dithiols[J].Surface&Coatings Technology,2005,195(2):162-167)。
Embodiment 1
The preparation method of the CNTs composite material (CNTs AgNP) of a kind of nanometer of modified by silver of the present embodiment, specific steps
It is as follows:
(1) P-TES photo-grafting
It weighs 0.7g CNTs and is put into the P-TES alcoholic solution (0.8g/L) of 100ml simultaneously ultrasonic disperse 10min.Then it uses
Vacuum filtration device extraction CNTs is placed into vacuum oven and places 4h at 100 DEG C.Then it will be put into mortar grinder powdering,
It is 365nm, intensity of illumination 0.5J/cm that wavelength is placed on after uniformly spreading out2Ultraviolet light under irradiate 700s.Then, alcohol is used
Cleaning 8 times are filtered in Vacuum filtration device and removes extra P-TES, obtain the carbon nanotube (CNTs- of P-TES photo-grafting
PTES)。
(2) N-TES self assembly
CNTs-PTES prepared by step (1) is put into the N-TES aqueous solution (1g/L) of 100ml, and in magnetic stirring apparatus
Upper stirring at normal temperature 60min, takes mixed liquor to clean, and is evaporated the carbon nanotube (CNTs-P& for obtaining surface molecular graft modification
NTES), silver-plated prepare to be pre-.
(3) nanometer modified by silver
Weigh 4g SnCl2Deionized water solution with 0.8g hydrochloric acid configuration 200ml is as sensitizing solution, and by 50mg's
CNTs-P&NTES is added in sensitizing solution ultrasonic disperse 30 minutes, and mixed liquor is filtered and is cleaned solid powder 10 times, completes sensitization
Process.Later, sensitization carbon nanotube is put into glucose containing 4.5g, the 100ml deionized water of 0.4g tartaric acid and 10ml ethyl alcohol
In solution, and ultrasonic disperse 1h.For modified by silver CNTs-P&NTES, by 0.7g AgNO3It is added in 200ml deionized water,
And ammonium hydroxide is added dropwise until solution secondary clearing again.Then it is poured slowly into the mixed solution containing sensitization carbon nanotube, and at 25 DEG C
Lower ultrasonic disperse 1h.Then, overreaction is prevented with ice-water bath processing 30min.Finally, filtering and being dried in vacuo through 10 washings
For 24 hours, the CNTs composite material (CNTs AgNP) of nanometer modified by silver is obtained.
Following inspection has been carried out to the composite material of prepared carbon nano tube surface molecule graft modification and nanometer modified by silver
Survey characterization:
Morphology analysis: using transmission electron microscope (TEM) observation comparison TES, carbon nano tube surface changes before and after the processing.CNTs-P&
Transmission electron microscope (TEM) figure of carbon nanotube is as shown in Figure 1 before and after the synthesis schematic diagram of NTES and surface molecular graft modification.By scheming
1 as it can be seen that carbon nano tube surface has apparent attachment after TES processing.With the table of gained CNTs@AgNP after tem observation modified by silver
Face pattern, as a result as shown in Figure 2.It can be found that the apparent Argent grain in surface uniformly adheres to, and partial size is 5nm or so.
Constituent analysis: the CNTs-P&NTES obtained by after XPS analysis P-TES and N-TES grafting processing, as a result such as Fig. 3 institute
Show, there are C, O, N and Si elements N occurs in 398.9eV wherein there is the peak O 1s in the position 532eV for processing rear surface
There is the peak C 1s in 284.8eV in the peak 1s, and 153.2eV and 102.9eV then respectively correspond the peak Si 2s and Si 2p, and S element
Peak is corresponded in the appearance of the position 164.9eV, and C, O, N, Si and S element are the peculiar element of TES molecule, the original surface CNTs
Those elements are had no, illustrate that there is both TES molecules on the surface CNTs.XPS swarming fitting result such as (a), (b) institute in Fig. 4
Show, the fitting result of Fig. 4 (a) is shown, the peak S 2p there are two composition, corresponds respectively to the S-C key of N-TES strand outermost end altogether
Illustrate the success of N-TES self assembly positioned at the position of 163.8eV and 165.2eV with S-H key.The fitting result of Fig. 4 (b) is aobvious
Show, the peak Si 2p there are two composition, corresponds respectively to the Si-C key in the silane group of TES intramolecular, positioned at 101.8eV's altogether
Position.And positioned at the position 102.4eV, the Si-O-Si that hydrolytic polymerization is formed between TES.Aglow external spectrum test comparison is former
Beginning CNTs and CNTs-P&NTES, as a result as shown in figure 5, in 1131cm-1And 1511cm-1There is two absorption peaks at place, corresponding
The stretching vibration of C-N.And in 1511cm-1Place is then attributed to the stretching vibration of C=N.Meanwhile being located at 868cm-1And 623cm-1Then
It is corresponding with the vibration of Si-O-Si and C-S respectively.Illustrate that the TES modification of CNTs is successful.
Embodiment 2
The preparation method of the CNTs composite material (CNTs AgNP) of a kind of nanometer of modified by silver of the present embodiment, specific steps
It is as follows:
(1) P-TES photo-grafting
It weighs 0.3g CNTs and is put into the P-TES alcoholic solution (0.5g/L) of 100ml simultaneously ultrasonic disperse 10min.Then it uses
Vacuum filtration device extraction CNTs is placed into vacuum oven and places 4h at 100 DEG C.Then it will be put into mortar grinder powdering,
It is 256nm, intensity of illumination 0.1J/cm that wavelength is placed on after uniformly spreading out2Ultraviolet light under irradiate 300s.Then, alcohol is used
Cleaning 8 times are filtered in Vacuum filtration device and removes extra P-TES, obtain the carbon nanotube (CNTs- of P-TES photo-grafting
PTES)。
(2) N-TES self assembly
CNTs-PTES prepared by step (1) is put into the N-TES aqueous solution (0.5g/L) of 100ml, and in magnetic agitation
Stirring at normal temperature 40min on device, takes mixed liquor to clean, and is evaporated the carbon nanotube (CNTs-P& for obtaining surface molecular graft modification
NTES), silver-plated prepare to be pre-.
(3) nanometer modified by silver
Weigh 2g SnCl2Deionized water solution with 0.4g hydrochloric acid configuration 200ml is as sensitizing solution, and by 20mg's
CNTs-P&NTES is added in sensitizing solution ultrasonic disperse 30 minutes, and mixed liquor is filtered and is cleaned solid powder 10 times, completes sensitization
Process.Later, sensitization carbon nanotube is put into glucose containing 20g, the 100ml deionized water solution of 2g tartaric acid and 5ml ethyl alcohol
In, and ultrasonic disperse 1h.For modified by silver CNTs-P&NTES, by 0.5g AgNO3It is added in 200ml deionized water, and drips
Add ammonium hydroxide until solution secondary clearing again.Then it is poured slowly into the mixed solution containing sensitization carbon nanotube, and surpass at 25 DEG C
Sound disperses 1h.Then, overreaction is prevented with ice-water bath processing 20min.Finally, 12h is filtered and is dried in vacuo through 10 washings,
Obtain the CNTs composite material (CNTs AgNP) of nanometer modified by silver.
Following inspection has been carried out to the composite material of prepared carbon nano tube surface molecule graft modification and nanometer modified by silver
Survey characterization:
Morphology analysis: it P-TES and N-TES grafting processing schematic and treated pattern: is seen using transmission electron microscope (TEM)
Examining comparison TES, surface changes before and after the processing, and discovery TES processing rear surface has apparent attachment.
Constituent analysis: with XPS analysis P-TES and N-TES grafting treated CNTs.Have found N, S, Si characteristic element is simultaneously
C-N is fitted, the features key such as Si-O-Si, C=N illustrates the successful grafting of TES.
Morphology analysis: CNTs surface topography after tem observation modified by silver is used, it can be found that the apparent Argent grain in surface is uniformly attached
?.
Embodiment 3
The preparation method of the CNTs composite material (CNTs AgNP) of a kind of nanometer of modified by silver of the present embodiment, specific steps
It is as follows:
(1) P-TES photo-grafting
It weighs 1g CNTs and is put into the P-TES alcoholic solution (1g/L) of 100ml simultaneously ultrasonic disperse 10min.Then vacuum is used
Suction filtration device extraction CNTs is placed into vacuum oven and places 4h at 100 DEG C.Then it will be put into mortar grinder powdering, uniformly
It is 300nm, intensity of illumination 1J/cm that wavelength is placed on after spreading out2Ultraviolet light under irradiate 500s.Then, with alcohol in vacuum
Cleaning 8 times are filtered in Suction filtration device and removes extra P-TES, obtain the carbon nanotube (CNTs-PTES) of P-TES photo-grafting.
(2) N-TES self assembly
CNTs-PTES prepared by step (1) is put into the N-TES aqueous solution (2g/L) of 100ml, and in magnetic stirring apparatus
Upper stirring at normal temperature 60min, takes mixed liquor to clean, and is evaporated the carbon nanotube (CNTs-P& for obtaining surface molecular graft modification
NTES), silver-plated prepare to be pre-.
(3) nanometer modified by silver
Weigh 4g SnCl2Deionized water solution with 0.8g hydrochloric acid configuration 200ml is as sensitizing solution, and by 50mg's
CNTs-P&NTES is added in sensitizing solution ultrasonic disperse 30 minutes, and mixed liquor is filtered and is cleaned solid powder 10 times, completes sensitization
Process.Later, sensitization carbon nanotube is put into glucose containing 5g, and the 100ml deionization of 0.6g tartaric acid and 15ml ethyl alcohol is water-soluble
In liquid, and ultrasonic disperse 1h.For modified by silver CNTs-P&NTES, by 1g AgNO3It is added in 200ml deionized water, and drips
Add ammonium hydroxide until solution secondary clearing again.Then it is poured slowly into the mixed solution containing sensitization carbon nanotube, and surpass at 25 DEG C
Sound disperses 1h.Then, overreaction is prevented with ice-water bath processing 60min.Finally, 36h is filtered and is dried in vacuo through 10 washings,
Obtain the CNTs composite material (CNTs AgNP) of nanometer modified by silver.
Following inspection has been carried out to the composite material of prepared carbon nano tube surface molecule graft modification and nanometer modified by silver
Survey characterization:
Morphology analysis: it P-TES and N-TES grafting processing schematic and treated pattern: is seen using transmission electron microscope (TEM)
Examining comparison TES, surface changes before and after the processing, and discovery TES processing rear surface has apparent attachment.
Constituent analysis: with XPS analysis P-TES and N-TES grafting treated CNTs.Have found N, S, Si characteristic element is simultaneously
C-N is fitted, the features key such as Si-O-Si, C=N illustrates the successful grafting of TES.
Morphology analysis: CNTs surface topography after tem observation modified by silver is used, it can be found that the apparent Argent grain in surface is uniformly attached
?.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver, it is characterised in that including following preparation step:
(1) carbon nanotube P-TES photo-grafting:
CNTs is added to ultrasonic disperse in P-TES alcoholic solution to react, solid product is separated, dried, then in ultraviolet light
UV-induced grafting is carried out according under the conditions of, obtains CNTs-PTES；
(2) N-TES self assembly:
CNTs-PTES prepared by step (1) is added in N-TES aqueous solution and is stirred to react, the mixed liquor after reaction is cleaned,
It is evaporated to get CNTs-P&NTES is arrived；
(3) nanometer modified by silver:
CNTs-P&NTES obtained by step (2) is added in sensitizing solution and carries out sensitized reaction, then the product after sensitization is added
Into reducing agent solution, ultrasonic mixing is uniform, obtains mixed liquor, then gained mixed liquor is added to ultrasonic mixing in silver ammino solution
Reaction, product are separated, washed, dried, and obtain the CNTs composite material of nanometer modified by silver.
2. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly it is 2~10g/L, P-TES in the P-TES alcoholic solution that CNTs described in (1), which is added to the concentration in P-TES alcoholic solution,
Concentration be 0.5~0.8g/L；The time of the ultrasonic disperse reaction is 10~30min.
3. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly solid product described in (1) is separated, dries and refer to after vacuum filtration in the dry 4~8h of 100 DEG C of vacuum ovens.
4. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that step
Suddenly ultraviolet irradiation condition described in (1) are as follows: a length of 256~365nm of ultraviolet light wave, intensity of illumination are 0.1~2J/cm2, when illumination
Between be 300~700s.
5. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly the concentration of N-TES aqueous solution described in (2) is 0.5~3g/L；It is described be stirred to react refer to stirring at normal temperature reaction 40~
80min。
6. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly sensitizing solution described in (3) refers to containing 10~30g/L SnCl2With the aqueous solution of 2~8g/L hydrochloric acid.
7. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly reducing agent solution described in (3) refers to containing 20~50g/L glucose, 20~50g/L tartaric acid and 50~100ml/L ethyl alcohol
Aqueous solution.
8. the preparation method of the CNTs composite material of a kind of nanometer of modified by silver according to claim 1, it is characterised in that: step
Suddenly ultrasonic mixing described in (3) reaction temperature be 25 DEG C, the time be 1~2h, after the reaction was completed with ice-water bath processing 30~
60min prevents overreaction.
9. the CNTs composite material of a kind of nanometer of modified by silver, it is characterised in that: pass through side according to any one of claims 1 to 8
Method is prepared.
10. application of the CNTs composite material of as claimed in claim 9 nanometer of modified by silver in flexible electronic device.
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