CN110305353A - Starch base bottom AgNW/PEDOT flexible conductive film and preparation method thereof - Google Patents
Starch base bottom AgNW/PEDOT flexible conductive film and preparation method thereof Download PDFInfo
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/0806—Silver
Abstract
The invention discloses a kind of starch base bottom AgNW/PEDOT flexible conductive films and preparation method thereof, and described method includes following steps: (1) preparing starch basilar memebrane；(2) it is electro-hydraulic to prepare composite guide；(3) flexible conductive film is prepared.The starch base bottom AgNW/PEDOT flexible conductive film of the method preparation, by the charge carrier transport between conducting polymer chain and metal nanometer line, the bulk conductivity of hybridized film can be significantly improved, this helps to carry out charge transmission by Spectrametry of Electron Exchange mechanism.This electric charge transfer is flowed into further through the fermi level in effectively pin valence band and the electric charge carrier from nano metal, the conductivity of starch base bottom AgNW/PEDOT flexible conductive film is caused to increase, electric conductivity is higher than the starch base bottom AgNW conductive film of same deposition density.
Description
Technical field
The present invention relates to macromolecule conductive film technical field of composite materials, and in particular to a kind of starch base bottom AgNW/PEDOT
Flexible conductive film and preparation method thereof.
Background technique
With the quickening of electronic product renewal speed, flexible electronics because its is light-weight, foldable, non-breakable, just
In transport, equipment investment are few the advantages that more and more attention has been paid to.Current most widely used flexible liner counterdie has PET film, poly- carbon
Sour (PC), polyvinyl alcohol (PVA) etc., but these materials are petrochemicals, it is not degradable, it is non-renewable, it easily causes tight
The environment and ecological problem of weight, and in order to realize that basilar memebrane is preferably combined with conductive material, it usually needs to flexible substrate surface
Active processing is carried out, this not only increases cost, it is also possible to reduce the light transmittance of basilar memebrane.
Transparent conductive metallic film mainly includes Ag, Au and Cu etc., this metalloid thin film is dense due to its free carrier
Degree about 1020A/cm3, there is very strong absorption in visible region, therefore to be prepared into transparent electrode, it is desirable that is deposited is thin
Film is very thin, and thickness is generally in 10nm or so.Film is too thick, and transmitance is then very low；Too thin, metallic film has then been hardly formed
Whole film exists in the form of island, causes film that there is very high resistivity and reflectivity therefore to prepare high quality
Transparent conductive metallic film difficulty is challenging.
Tin indium oxide (ITO) is applied widely as traditional transparent conductive material in industry, still, phosphide element
Content in the earth's crust is extremely low, its can supply decline year by year, and ITO material stiffness is strong, and the easy fracture under bending stress causes
ITO is difficult to the application demand of the competent following flexible transparent conductive film.The alternative solution potential as ITO, metal nano
Line, metal grill, carbon nanotube, graphene are by numerous studies.It is studied both at home and abroad by one-dimensional metal conductive material silver nanowires
It is embedded in starch basilar memebrane, prepares starch base bottom silver nanowires flexible transparent conducting film, realizes biomass material and photoelectric material
Combination.But since silver nanowires is loosely overlapped in starch basement membrane surface, conductive film mechanical stability is not only influenced, it is also made
Roughness increase easily leads to photoelectric device short circuit, and furthermore silver nanowires exposes easy to oxidize in air and square resistance is caused to increase
Greatly.
Summary of the invention
In order to solve the problems, such as prior art problem and deficiency, the purpose of the present invention is to provide a kind of starch bases
Bottom AgNW/PEDOT flexible conductive film and preparation method thereof.
The purpose of the present invention is realized at least through one of following technical solution.
The present invention provides a kind of preparation methods of starch base bottom AgNW/PEDOT flexible conductive film, include the following steps:
(1) it prepares starch basilar memebrane: starch being added in deionized water, starch solution is obtained, three is added into starch solution
Chlorethoxyfos stir, and gelatinization adds ethylene glycol, stirring, ultrasonication, centrifugation obtain starch milk solution, by starch milk solution
Film forming, drying, obtains starch basilar memebrane；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid is added in ethylene glycol
(PEDOT:PSS) in solution, ultrasonication obtains organic conductive liquid；Organic conductive liquid and silver nanowires (AgNW) solution is mixed
It closes, it is electro-hydraulic to obtain composite guide；
(3) prepare flexible conductive film: a dropping step (2) obtains compound on the starch basilar memebrane for obtaining step (1)
Conduction liquid, spin coating is dry, obtains starch base bottom AgNW/PEDOT flexible conductive film.
Preferably, starch and the mass ratio of deionized water are 5%-7% in step (1) starch solution；The body of phosphorus oxychloride
The long-pending mass ratio with starch is (0.1-0.2) mL/g；The temperature of the gelatinization is 80-100 DEG C, time 0.5-2h；Ethylene glycol
Volume and starch mass ratio be (0.3-0.6) mL/g；The temperature of the drying is 40-60 DEG C, and the time of drying is 10-
15h。
Preferably, the mass concentration of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid solution is in step (2)
(0.5-1)g/ml；The volume ratio of ethylene glycol and poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is 2%-10%；
The solvent of silver nanowires solution is deionized water, and the diameter of silver nanowires is 40-80nm；Silver nanowires solution it is dense
Degree is (2-12) mg/ml；The volume ratio of organic conductive liquid and silver nanowires solution is 2%-10%.
Preferably, spin coating described in step (3), which refers to, is cut into the circle that radius is 1.5-2.5cm for starch basilar memebrane, so
It is placed on spin coating instrument sucker, at 500-2000r/min spin coating 10- electro-hydraulic in the circular the center point dropwise addition composite guide
20s；The temperature of the drying is 20-40 DEG C, time 10-20h；The settled density of silver nanowires is in the flexible conductive film
100-500mg/m2。
Preferably, the stirring is magnetic stirring apparatus, and the magnetic stirring apparatus is 85-2 type magnetic stirring apparatus, stirring
Revolving speed be 100-300r/min；The temperature of stirring is 20-35 DEG C；The time of stirring is 20-40min.
Preferably, that the ultrasound is KQ-250DE type numerical control ultrasonic cleaner, 100-300W ultrasonication 20-
60min。
Preferably, the centrifugation is 3000-6000r/min using L-550 desk centrifuge, the revolving speed of centrifugation, from
The time of the heart is 5-10min；
Preferably, the spin coating uses WS-650Mz-23NPPB type spin coating spin coating instrument, spin coating 10- under 500-2000r/min
20s。
Preferably, the method for the film forming is the tape casting.
The present invention also provides a kind of shallow lakes of the preparation method of starch base bottom AgNW/PEDOT flexible conductive film preparation
Powder substrate AgNW/PEDOT flexible conductive film.
The present invention is based on the principle that (3,4- ethene dioxythiophene)-polyphenyl poly- in AgNW/PEDOT flexible conductive film
Vinyl sulfonic acid (PEDOT:PSS) solution has filled up the AgNW hole in AgNW conductive film, forms one on AgNW reticular structure surface
The film of layer glossy clear, significantly reduces its surface roughness, also plays fixed function to AgNW, to improve membrane structure
Stability and oxidation stability, the circulation in addition, carrier jumps between organic PEDOT film and inorganic AgNW, make Thin film conductive.
PEDOT chain chemistry participates in AgNWs network.The quinoid structure of PEDOT chain is converted into benzenoid structure, is more advantageous to electricity
Lotus is transmitted in interchain and chain, and electronics is transferred to PEDOT from conductive PEDOT chain tra nsfer to silver nanowires or from silver nanowires, from
And improve electric conductivity.
Compared to the prior art, the invention has the advantages that and advantage:
(1) starch base bottom AgNW/PEDOT flexible conductive film provided by the invention and current most widely used flexible substrate
Film: PET film, poly- carbonic acid (PC), polyvinyl alcohol (PVA) etc. are compared, have it is natural, renewable, degradable, do not easily cause it is serious
The advantages such as environment and ecological problem.Current useful cellulose and graphene prepare the report of conductive film, but cellulose is less soluble
Solution, and most of cellulose solvents are expensive, recycling is difficult.Starch basilar memebrane with high surface is used as naturally can be again
Raw degradable electrically conducting transparent basilar memebrane, in flexible electronics, the fields such as polymer composite possess wide application
Prospect；
(2) starch base bottom AgNW/PEDOT flexible conductive film provided by the invention, is received by conducting polymer chain and metal
The bulk conductivity of charge carrier transport between rice noodles, hybridized film can significantly improve, this facilitates through Spectrametry of Electron Exchange machine
System carries out charge transmission.This electric charge transfer is further through the fermi level in effectively pin valence band and from the charge of nano metal
Carrier flows into, and the conductivity of starch base bottom AgNW/PEDOT flexible conductive film is caused to increase, and electric conductivity is higher than identical heavy
The starch base bottom AgNW conductive film of product density.
Detailed description of the invention
Fig. 1 is the SEM figure of starch base bottom AgNW/PEDOT compliant conductive film surface prepared by embodiment 1；
Fig. 2 is starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5 and shallow lake prepared by comparative example 1 to 5
The variation comparison diagram of the electric conductivity (conductive sheet resistance) of powder substrate AgNW conductive film；
Fig. 3 is starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5 and shallow lake prepared by comparative example 1 to 5
The variation comparison diagram of the light transmittance of powder substrate AgNW conductive film；
Fig. 4 is the starch base bottom AgNW/PEDOT flexible conductive film sheet resistance of the preparation of embodiment 1 to 5 with the variation of number of bends
Comparison diagram；
Fig. 5 is the ambient stable performance comparison of starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5
Figure；
Fig. 6 is the starch base bottom AgNW/PEDOT flexible conductive film and starch basilar memebrane of raw starch, the preparation of embodiment 2
Thermodynamically stable performance comparison diagram.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment, the invention will be further described, but the present invention claims
The range of protection is not limited to the range of embodiment expression.
Embodiment 1
Present embodiments provide a kind of preparation method of starch base bottom AgNW/PEDOT flexible conductive film, including following step
It is rapid:
(1) starch basilar memebrane is prepared:
3g potato dried starch is weighed in reactor, 50g deionized water 300r/min magnetic agitation at 35 DEG C is added
20min is uniformly mixed, is configured to starch solution, and 0.3ml phosphorus oxychloride, the 300r/min at 35 DEG C are added into starch solution
Magnetic agitation 20min is uniformly mixed, be placed in water-bath 100 DEG C at a temperature of be gelatinized 30min, add 0.9ml second two
Alcohol stirs, is centrifuged 5min under the revolving speed of 100W ultrasonication 60min, 6000r/min, obtains starch milk solution, take 20ml starch
Milk solution is in the polystyrene culture dish that diameter is 10cm, the tape casting film forming, dries 12h in 40 DEG C of baking oven, obtains starch base bottom
Film；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is added in ethylene glycol
In, wherein the volume of ethylene glycol is the 5% of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid liquor capacity, poly- (3,4- second
Alkene dioxy thiophene)-polystyrolsulfon acid solution concentration be 0.7g/ml；100W ultrasonication 60min is uniformly mixed it,
Obtain organic conductive liquid；Organic conductive liquid is mixed with the silver nanowires solution of 51uL, it is electro-hydraulic to obtain composite guide, wherein organic conductive liquid
Volume be silver nanowires solution volume 5%, the diameter of silver nanowires is 80nm；The concentration of silver nanowires solution is 2mg/
ml；
(3) it prepares flexible conductive film: to deionized water is added in the culture dish of carrying starch basilar memebrane in step (1), soaking
10min is steeped, the starch basilar memebrane of wetting is removed, starch basilar memebrane is cut into the circle that radius is 1.8cm and is placed in spin coating instrument sucker
On, a dropping step (2) resulting composite guide is electro-hydraulic on starch basilar memebrane, then spin coating 10s under 1000r/min is put in 30 DEG C
Dry 15h, obtaining silver nanowires settled density is 100mg/m2Starch base bottom AgNW/PEDOT flexible conductive film.
Comparative example 1
This comparative example contrastingly proposes a kind of preparation method of starch base bottom AgNW conductive film and the side of embodiment 1
Method step is identical with raw material dosage parameter, unique the difference is that being added without poly- (3,4-rthylene dioxythiophene)-polyphenyl in step (2)
Vinyl sulfonic acid solution, it is 100mg/m that the method, which is prepared into silver nanowires settled density,2Starch base bottom AgNW conductive film.
Embodiment 2
Present embodiments provide a kind of preparation method of starch base bottom AgNW/PEDOT flexible conductive film, including following step
It is rapid:
(1) starch basilar memebrane is prepared:
3.5g potato dried starch is weighed in reactor, 50g deionized water is added, 200r/min magnetic force stirs at 30 DEG C
30min is mixed, is uniformly mixed, is configured to starch solution, 0.6ml phosphorus oxychloride, the 200r/ at 30 DEG C are added into starch solution
Min magnetic agitation 30min is uniformly mixed, be placed in water-bath 90 DEG C at a temperature of be gelatinized 30min, add 2.1ml second two
Alcohol stirs, is centrifuged 6min under the revolving speed of 150W ultrasonication 40min, 5000r/min, obtains starch milk solution, take 20ml starch
Milk solution is in the polystyrene culture dish that diameter is 10cm, the tape casting film forming, dries 20h in 40 DEG C of baking oven, obtains starch base bottom
Film；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is added in ethylene glycol
In, wherein the volume of ethylene glycol is the 2% of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid liquor capacity, poly- (3,4- second
Alkene dioxy thiophene)-polystyrolsulfon acid solution concentration be 0.5g/ml；150W ultrasonication 40min is uniformly mixed it,
Obtain organic conductive liquid；Organic conductive liquid is mixed with the silver nanowires solution of 71uL, it is electro-hydraulic to obtain composite guide, wherein organic conductive liquid
Volume be silver nanowires solution volume 10%, the diameter of silver nanowires is 70nm；The concentration of silver nanowires solution is
2mg/ml；
(3) it prepares flexible conductive film: to deionized water is added in the culture dish of carrying starch basilar memebrane in step (1), soaking
10min is steeped, the starch basilar memebrane of wetting is removed, starch basilar memebrane is cut into the circle that radius is 1.5cm and is placed in spin coating instrument sucker
On, a dropping step (2) resulting composite guide is electro-hydraulic on starch basilar memebrane, then spin coating 10s under 2000r/min is put in 40 DEG C
Dry 10h, obtaining silver nanowires settled density is 200mg/m2Starch base bottom AgNW/PEDOT flexible conductive film.
Comparative example 2
This comparative example contrastingly proposes a kind of preparation method of starch base bottom AgNW conductive film and the side of embodiment 1
Method step is identical with raw material dosage parameter, unique the difference is that being added without poly- (3,4-rthylene dioxythiophene)-polyphenyl in step (2)
Vinyl sulfonic acid solution, it is 200mg/m that the method, which is prepared into silver nanowires settled density,2Starch base bottom AgNW conductive film.
Embodiment 3
Present embodiments provide a kind of preparation method of starch base bottom AgNW/PEDOT flexible conductive film, including following step
It is rapid:
(1) starch basilar memebrane is prepared:
2.7g potato dried starch is weighed in reactor, 50g deionized water is added, 300r/min magnetic force stirs at 30 DEG C
20min is mixed, is uniformly mixed, is configured to starch solution, 0.3ml phosphorus oxychloride, the 300r/ at 30 DEG C are added into starch solution
Min magnetic agitation 20min is uniformly mixed, be placed in water-bath 80 DEG C at a temperature of be gelatinized 60min, add 1.5ml second two
Alcohol stirs, is centrifuged 8min under the revolving speed of 200W ultrasonication 30min, 4000r/min, obtains starch milk solution, take 20ml starch
Milk solution is in the polystyrene culture dish that diameter is 10cm, the tape casting film forming, dries 10h in 50 DEG C of baking oven, obtains starch base bottom
Film；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is added in ethylene glycol
In, wherein the volume of ethylene glycol is the 5% of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid liquor capacity, poly- (3,4- second
Alkene dioxy thiophene)-polystyrolsulfon acid solution concentration be 0.8g/ml；200W ultrasonication 30min is uniformly mixed it,
Obtain organic conductive liquid；Organic conductive liquid is mixed with the silver nanowires solution of 74uL, it is electro-hydraulic to obtain composite guide, wherein organic conductive liquid
Volume be silver nanowires solution volume 2%, the diameter of silver nanowires is 60nm；The concentration of silver nanowires solution is
8mg/ml；
(3) it prepares flexible conductive film: to deionized water is added in the culture dish of carrying starch basilar memebrane in step (1), soaking
10min is steeped, the starch basilar memebrane of wetting is removed, starch basilar memebrane is cut into the circle that radius is 2.5cm and is placed in spin coating instrument sucker
On, a dropping step (2) resulting composite guide is electro-hydraulic on starch basilar memebrane, spin coating 20s under 500r/min, is then put in 20 DEG C and does
Dry 20h, obtaining silver nanowires settled density is 300mg/m2Starch base bottom AgNW/PEDOT flexible conductive film.
Comparative example 3
This comparative example contrastingly proposes a kind of preparation method of starch base bottom AgNW conductive film and the side of embodiment 1
Method step is identical with raw material dosage parameter, unique the difference is that being added without poly- (3,4-rthylene dioxythiophene)-polyphenyl in step (2)
Vinyl sulfonic acid solution, it is 300mg/m that the method, which is prepared into silver nanowires settled density,2Starch base bottom AgNW conductive film.
Embodiment 4
Present embodiments provide a kind of preparation method of starch base bottom AgNW/PEDOT flexible conductive film, including following step
It is rapid:
(1) starch basilar memebrane is prepared:
3g potato dried starch is weighed in reactor, 50g deionized water, the 200r/min magnetic agitation at 25 DEG C is added
30min is uniformly mixed, is configured to starch solution, and 0.6ml phosphorus oxychloride, the 200r/min at 25 DEG C are added into starch solution
Magnetic agitation 30min is uniformly mixed, be placed in water-bath 90 DEG C at a temperature of be gelatinized 90min, add 1.7ml ethylene glycol,
It stirs, be centrifuged 8min under the revolving speed of 250W ultrasonication 30min, 4000r/min, obtain starch milk solution, take 20ml starch milk
Solution is in the polystyrene culture dish that diameter is 10cm, the tape casting film forming, dries 12h in 60 DEG C of baking oven, obtains starch basilar memebrane；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is added in ethylene glycol
In, wherein the volume of ethylene glycol is the 8% of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid liquor capacity, poly- (3,4- second
Alkene dioxy thiophene)-polystyrolsulfon acid solution concentration be 0.9g/ml；250W ultrasonication 30min is uniformly mixed it,
Obtain organic conductive liquid；Organic conductive liquid is mixed with the silver nanowires solution of 50ul, it is electro-hydraulic to obtain composite guide, wherein organic conductive liquid
Volume be silver nanowires solution volume 8%, the diameter of silver nanowires is 50nm；The concentration of silver nanowires solution is
10mg/ml；
(3) it prepares flexible conductive film: to deionized water is added in the culture dish of carrying starch basilar memebrane in step (1), soaking
10min is steeped, the starch basilar memebrane of wetting is removed, starch basilar memebrane is cut into the circle that radius is 2cm and is placed on spin coating instrument sucker,
A dropping step (2) resulting composite guide is electro-hydraulic on starch basilar memebrane, then spin coating 15s under 1500r/min is put in 35 DEG C of dryings
15h, obtaining silver nanowires settled density is 400mg/m2Starch base bottom AgNW/PEDOT flexible conductive film.
Comparative example 4
This comparative example contrastingly proposes a kind of preparation method of starch base bottom AgNW conductive film and the side of embodiment 1
Method step is identical with raw material dosage parameter, unique the difference is that being added without poly- (3,4-rthylene dioxythiophene)-polyphenyl in step (2)
Vinyl sulfonic acid solution, it is 400mg/m that the method, which is prepared into silver nanowires settled density,2Starch base bottom AgNW conductive film.
Embodiment 5
Present embodiments provide a kind of preparation method of starch base bottom AgNW/PEDOT flexible conductive film, including following step
It is rapid:
(1) starch basilar memebrane is prepared:
2.5g potato dried starch is weighed in reactor, 50g deionized water is added, 100r/min magnetic force stirs at 20 DEG C
40min is mixed, is uniformly mixed, is configured to starch solution, 0.5ml phosphorus oxychloride, the 100r/ at 20 DEG C are added into starch solution
Min magnetic agitation 40min is uniformly mixed, be placed in water-bath 80 DEG C at a temperature of be gelatinized 120min, add 1ml second two
Alcohol stirs, is centrifuged 10min under the revolving speed of 300W ultrasonication 20min, 3000r/min, obtains starch milk solution, 20ml is taken to form sediment
Powder milk solution is in the polystyrene culture dish that diameter is 10cm, the tape casting film forming, dries 12h in 40 DEG C of baking oven, obtains starch base
Counterdie；
(2) it is electro-hydraulic to prepare composite guide: poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution is added in ethylene glycol
In, wherein the volume of ethylene glycol is the 10% of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid liquor capacity, poly- (3,4-
Ethene dioxythiophene)-polystyrolsulfon acid solution concentration be 1g/ml；300W ultrasonication 20min is uniformly mixed it,
Obtain organic conductive liquid；Organic conductive liquid is mixed with the silver nanowires solution of 70uL, it is electro-hydraulic to obtain composite guide, wherein organic conductive liquid
Volume be silver nanowires solution volume 5%, the diameter of silver nanowires is 40nm；The concentration of silver nanowires solution is
12mg/ml；
(3) it prepares flexible conductive film: to deionized water is added in the culture dish of carrying starch basilar memebrane in step (1), soaking
10min is steeped, the starch basilar memebrane of wetting is removed, starch basilar memebrane is cut into the circle that radius is 2.3cm and is placed in spin coating instrument sucker
On, a dropping step (2) resulting composite guide is electro-hydraulic on starch basilar memebrane, then spin coating 10s under 1500r/min is put in 25 DEG C
Dry 18h, obtaining silver nanowires settled density is 500mg/m2Starch base bottom AgNW/PEDOT flexible conductive film.
Comparative example 5
This comparative example contrastingly proposes a kind of preparation method of starch base bottom AgNW conductive film and the side of embodiment 1
Method step is identical with raw material dosage parameter, unique the difference is that being added without poly- (3,4-rthylene dioxythiophene)-polyphenyl in step (2)
Vinyl sulfonic acid solution, it is 500mg/m that the method, which is prepared into silver nanowires settled density,2Starch base bottom AgNW conductive film.
Fig. 1 is the SEM figure of starch base bottom AgNW/PEDOT compliant conductive film surface prepared by embodiment 1, can from Fig. 1
Out, PEDOT:PSS has filled up AgNW hole in AgNW/PEDOT conductive film, AgNW reticular structure surface formed one layer it is smooth
Bright film significantly reduces its surface roughness, also plays fixed function to AgNW, thus improve membrane structure stability and
Environmental stability.
Fig. 2 is starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5 and shallow lake prepared by comparative example 1 to 5
The variation comparison diagram of the electric conductivity (conductive sheet resistance) of powder substrate AgNW conductive film compares starch base bottom AgNW conductive film, from Fig. 2
As can be seen that the two sheet resistance all increases with AgNW settled density and reduced, but reduction rate is more and more slower, is finally intended to put down
Weighing apparatus is low in contrast to same deposition density AgNW, AgNW/PEDOT conductive film ratio AgNW conductive film sheet resistance.
Fig. 3 is starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5 and shallow lake prepared by comparative example 1 to 5
The variation comparison diagram of light transmittance of the powder substrate AgNW conductive film at 550nm compares starch base bottom AgNW conductive film, can from Fig. 3
To find out, AgNW conductive film light transmittance and silver nanowires settled density are in simple linear relationship, i.e., as silver nanowires deposition is close
The increase of degree, two kinds of conductive film light transmittance uniform descents at 550nm, but straight slope becomes larger, and reduces speed and becomes faster.
Fig. 4 is the starch base bottom AgNW/PEDOT flexible conductive film sheet resistance of the preparation of embodiment 1 to 5 with the variation of number of bends
Comparison diagram, from fig. 4, it can be seen that the sheet resistance of AgNW/PEDOT flexible conductive film increases less than 2% with the increase of number of bends,
PEDOT:PSS strand has fixed function to AgNW, enhances its mechanical stability.
Fig. 5 is the ambient stable performance comparison of starch base bottom AgNW/PEDOT flexible conductive film prepared by embodiment 1 to 5
Figure places 100 days rear resistives in air as shown in figure 5, from fig. 5, it can be seen that with number of days is placed in air
Increase, though the sheet resistance of AgNW/PEDOT flexible conductive film slightly has increase, variable quantity is lower than 5%.
Fig. 6 is the starch base bottom AgNW/PEDOT flexible conductive film and starch basilar memebrane of raw starch, the preparation of embodiment 2
Thermodynamically stable performance comparison diagram compares the thermogravimetric analysis of raw starch and starch basilar memebrane, as can be seen from Figure 6, starch base
Apparent thermal degradation does not occur, is conducive to shallow lake before 250 DEG C for bottom AgNW/PEDOT flexible conductive film and starch basilar memebrane
Powder basilar memebrane carries out further high-temperature electric conduction processing.
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 starch base bottom AgNW/PEDOT flexible conductive film, which comprises the steps of:
(1) it prepares starch basilar memebrane: starch being added in deionized water, starch solution is obtained, trichlorine oxygen is added into starch solution
Phosphorus stirs, and gelatinization adds ethylene glycol, and stirring, ultrasonication, centrifugation obtain starch milk solution, by starch milk solution film forming,
Drying, obtains starch basilar memebrane；
(2) it is electro-hydraulic to prepare composite guide: ethylene glycol is added in poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid solution, surpasses
Sonicated obtains organic conductive liquid；Organic conductive liquid is mixed with silver nanowires solution, it is electro-hydraulic to obtain composite guide；
(3) flexible conductive film is prepared: the composite conducting that a dropping step (2) obtains on the starch basilar memebrane for obtaining step (1)
Liquid, spin coating is dry, obtains starch base bottom AgNW/PEDOT flexible conductive film.
2. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that step
(1) starch and the mass ratio of deionized water are 5%-7% in starch solution；The volume of phosphorus oxychloride and the mass ratio of starch are 0.1-
0.2mL/g；The temperature of the gelatinization is 80-100 DEG C, time 0.5-2h；
The volume of ethylene glycol and the mass ratio of starch are 0.3-0.6mL/g；The temperature of the drying be 40-60 DEG C, drying when
Between be 10-15h.
3. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that step
(2) mass concentration of (3,4- ethene dioxythiophene)-polystyrolsulfon acid solution poly- in is 0.5-1g/ml；Ethylene glycol and it is poly- (3,
4- ethene dioxythiophene)-polystyrolsulfon acid solution volume ratio be 2%-10%；
The solvent of silver nanowires solution is deionized water, and the diameter of silver nanowires is 40-80nm；The concentration of silver nanowires solution is
(2-12) mg/ml；The volume ratio of organic conductive liquid and silver nanowires solution is 2%-10%.
4. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that step
(3) spin coating described in, which refers to, is cut into the circle that radius is 1.5-2.5cm for starch basilar memebrane, is subsequently placed on spin coating instrument sucker,
Electro-hydraulic, the spin coating 10-20 s at 500-2000r/min in the circular the center point dropwise addition composite guide；The temperature of the drying
It is 20-40 DEG C, time 10-20h；The settled density of silver nanowires is 100-500mg/m in the flexible conductive film2。
5. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that described
Stirring is magnetic stirring apparatus, and the magnetic stirring apparatus is 85-2 type magnetic stirring apparatus, and the revolving speed of stirring is 100-300r/
min；The temperature of stirring is 20-35 DEG C；The time of stirring is 20-40min.
6. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that described
Ultrasound is KQ-250DE type numerical control ultrasonic cleaner, 100-300W ultrasonication 20-60min.
7. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that described
Using L-550 desk centrifuge, the revolving speed of centrifugation is 3000-6000r/min for centrifugation, and the time of centrifugation is 5-10min.
8. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that described
Spin coating uses WS-650Mz-23NPPB type spin coating spin coating instrument, spin coating 10-20 s under 500-2000r/min.
9. the preparation method of starch base bottom AgNW/PEDOT flexible conductive film according to claim 1, which is characterized in that described
The method of film forming is the tape casting.
10. the starch of the preparation method preparation of any one of claim 1 to the 9 starch base bottom AgNW/PEDOT flexible conductive film
Substrate AgNW/PEDOT flexible conductive film.
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