CN108933004A - A kind of biomass nano cellulose conductive composite film and preparation method thereof - Google Patents
A kind of biomass nano cellulose conductive composite film and preparation method thereof Download PDFInfo
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- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The present invention provides a kind of preparation methods of biomass nano cellulose conductive composite film, belong to conductive material technical field, and the present invention filters the aqueous suspension of biomass cellulose, obtain biomass fiber hydrogel filter membrane；Obtained biomass fiber hydrogel filter membrane is immersed into successively displacement, demoulding and the first drying in ethyl alcohol, obtains biomass cellulose paper；Obtained biomass cellulose paper is impregnated to be placed on silicon wafer in PMMA solution and carries out the second drying, obtains biomass cellulose laminated film；Obtained biomass cellulose laminated film is passed through into plasma clean, the biomass cellulose laminated film that obtains that treated；By the one side of the silver nanowires dispersant liquid drop biomass cellulose laminated film that is coated onto that treated, biomass nano cellulose conductive composite film is obtained.The biomass nano cellulose conductive composite film good conductivity that the present invention is prepared, transparency are high.
Description
Technical field
The present invention relates to conductive material technical field, in particular to a kind of biomass nano cellulose conductive composite film and
Preparation method.
Background technique
Cellulose separation and Extraction is come out from biomass material using chemistry, mechanical means, obtained nano-cellulose
With good mechanical property, high length-diameter ratio, surface not only active group rich in is easy to react and forms hydrogen bond or change
Key is learned, excellent mechanical strength and natural netted tangled structure are also possessed, the preparation for nano-cellulose laminated film is established
Basis.
Polymethyl methacrylate (PMMA) be so far synthesize transparent material in quality it is most excellent, price again relatively fit
Suitable kind, PMMA are dissolved in organic solvent, such as acetone, chloroform, methylene chloride, phenol, methyl phenyl ethers anisole, can be formed by spin coating
Good film has good dielectric properties.Transparent height can be obtained in conjunction with mushy nanofiber paper in PMMA, soft
Good toughness, mechanical property and the good laminated film of dielectric properties.
Metal nanometer line due on two-dimensional direction be in nanoscale, the quantum size effect that it has, skin effect,
The advantages such as dielectric effect are shown different from the macro properties such as the hot photoelectromagnetic of power of conventional material, " novel nano structural conductive
The photoelectric characteristic and application study of film " based on (Zhejiang University, Kou Pengfei) penetration theory to random AgNW (silver nanowires)
The photoelectricity performance of network has carried out theoretical research, with high mechanical strength, the advantages that good conductivity, large specific surface area.If
By metal nanometer line and biomass polymers Film laminated, the dielectric properties of film can be greatly improved, have it is transparent, it is flexible to lead
The comprehensive performances such as electricity, in modern flexible device, liquid crystal display, touch screens and other fields can be widely applied.But biomass polymers table
Face is nonpolarity and smooth, is difficult carried metal substance, therefore, in the prior art not by metal nanometer line and biomass polymers
The case of Film laminated.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of preparation sides of biomass nano cellulose conductive composite film
Method, biomass nano cellulose conductive composite film provided by the invention has successfully loaded silver nanowires, and good conductivity, transparent
Degree is high.
The present invention provides a kind of preparation methods of biomass nano cellulose conductive composite film, comprising the following steps:
1) aqueous suspension of biomass cellulose is filtered, obtains biomass fiber hydrogel；The biomass fiber
Hydrogel with a thickness of 0.5~1mm；
2) biomass fiber hydrogel that step 1) obtains is immersed in ethyl alcohol successively replaced, demoulding and first dry
It is dry, obtain biomass cellulose paper；
3) the biomass cellulose paper that step 2) obtains is impregnated in PMMA solution be placed on silicon wafer carry out it is second dry
It is dry, obtain biomass cellulose laminated film；
4) the biomass cellulose laminated film for obtaining step 3) passes through plasma clean, the biology that obtains that treated
Matter cellulose laminated film；
5) silver nanowires dispersant liquid drop is coated onto step 4) and obtains that treated the one of biomass cellulose laminated film
Face obtains biomass nano cellulose conductive composite film.
Preferably, the mass concentration of the aqueous suspension of biomass cellulose is 0.2~1% in the step 1).
Preferably, the temperature replaced in the step 2) is room temperature, and the displaced time is 8~14h.
Preferably, temperature dry in the step 2) is 50~70 DEG C, and the dry time is 2~5h.
Preferably, the mass concentration of PMMA solution is 20~30% in the step 3).
Preferably, the time impregnated in the step 3) is 12~for 24 hours.
Preferably, step 4) the plasma cleaning carries out in plasma washing machine, and the plasma is clear
The frequency 40KHZ of washing machine, power 600W, processing time are 3min.
Preferably, the mass concentration of silver nanowires dispersion liquid is 5~8mg/mL in the step 5).
Preferably, in the step 5) biomass cellulose laminated film to the load capacity of silver nanowires be 0.01~
0.2mg/cm2。
It is described the present invention also provides the biomass nano cellulose conductive composite film that above-mentioned preparation method is prepared
The silver nanowires load capacity of laminated film is 0.01~0.2mg/cm2, the laminated film with a thickness of 0.06~0.1mm.
Advantageous effects: the present invention filters biomass cellulose aqueous suspension, obtains biomass fiber hydrogel；
The biomass fiber hydrogel with a thickness of 0.5~1mm；Obtained cellulose aquagel is immersed in ethyl alcohol and is successively set
It changes, demoulding and first dry, obtains biomass cellulose paper；After obtained biomass cellulose paper is impregnated in PMMA solution
It is placed on silicon wafer and carries out the second drying, obtain biomass cellulose laminated film；The biomass cellulose laminated film that will be obtained
By plasma clean, the biomass cellulose laminated film that obtains that treated.Silver nanowires dispersant liquid drop is coated onto processing
The one side of biomass cellulose laminated film afterwards obtains biomass nano cellulose conductive composite film.The present invention by
The second drying and forming-film is carried out on silicon wafer, ensure that the planarization of composite material, by carrying out to biomass cellulose laminated film
Plasma cleaning stamps ion and fold in biomass cellulose laminated film on one side, is easy to load upper metal nanometer line.This
Inventing the biomass nano cellulose conductive composite film silver nanowires load capacity being prepared is 0.01~0.2mg/cm2,
Good conductivity, transparency is high, and flexibility is high.With the raising of silver nanowires load factor, the resistance of conductive composite film gradually drops
Low (6.0~0.1 × 103Ω/cm), light transmittance is gradually lowered (transmitance is 86~32% at 600nm wavelength).
Detailed description of the invention:
Fig. 1 is the pictorial diagram of biomass cellulose aqueous suspension in embodiment 1；
Fig. 2 is biomass cellulose aqueous suspension TEM figure in embodiment 1；Upper right corner illustration is sample specimens
Fig. 3 is the pictorial diagram of biomass cellulose paper obtained in embodiment 1；
Fig. 4 is the pictorial diagram of biomass cellulose laminated film in embodiment 1；
Fig. 5 is the pictorial diagram of biomass nano cellulose conductive composite film in embodiment 1；
Fig. 6 is the pictorial diagram of biomass nano cellulose conductive composite film in circuit in embodiment 1；
Fig. 7 is the light transmission curve of different silver nanowires load factors in 1~embodiment of embodiment 4.
Specific embodiment
The present invention provides a kind of preparation methods of biomass nano cellulose conductive composite film, comprising the following steps:
1) biomass cellulose aqueous suspension is filtered, obtains biomass fiber hydrogel；The biomass cellulose
Hydrogel with a thickness of 0.5~1mm；
2) the biomass fiber hydrogel for obtaining step 1) immerses successively displacement, demoulding and the first drying in ethyl alcohol,
Obtain biomass cellulose paper；
3) the biomass cellulose paper that step 2) obtains is impregnated in PMMA solution be placed on silicon wafer carry out it is second dry
It is dry, obtain biomass cellulose laminated film；
4) the biomass cellulose laminated film for obtaining step 3) passes through plasma clean, the biology that obtains that treated
Matter cellulose laminated film；
5) silver nanowires dispersant liquid drop is coated onto step 4) and obtains that treated the one of biomass cellulose laminated film
Face obtains biomass nano cellulose conductive composite film.
The present invention filters biomass cellulose aqueous suspension, obtains biomass fiber hydrogel；The biomass is fine
Tie up hydrogel with a thickness of 0.5~1mm.
In the present invention, the biomass cellulose is preferably the cellulose that biomass material is prepared.
In the present invention, the biomass material is preferably timber, bamboo wood, rice, campanulaceae or sugarcane.
In the present invention, the method that the biomass material prepares cellulose preferably includes following steps:
1) biomass material, sodium chlorite, glacial acetic acid and water are mixed into removing lignin, obtains the biology of removing lignin
Matter raw material；
2) biomass material for removing lignin is mixed with the potassium hydroxide solution of 2wt% and carries out alkali process, obtain alkali
Treated biomass material；
3) lignin is removed again after mixing biomass material, sodium chlorite, glacial acetic acid and the water after alkali process,
Obtain holocellulose；
4) obtained holocellulose is mixed into alkali process again with the potassium hydroxide solution of 5wt%, obtains purifying cellulose；
5) purifying cellulose is mixed to the sour processing of progress with the hydrochloric acid solution of 1wt%, obtains loose purifying cellulose.
Biomass material, sodium chlorite, glacial acetic acid and water are mixed removing lignin by the present invention, obtain removing lignin
Biomass material.
In the present invention, the amount ratio of the biomass material, sodium chlorite, glacial acetic acid and water be preferably 2g:0.7~
0.8g:0.5mL:65mL, more preferably 2g:0.75g:0.5mL:65mL.
In the present invention, the temperature of the removing lignin is preferably 70~80 DEG C, and more preferably 75 DEG C；The removing wood
The time of quality is preferably 4~10h, more preferably 5~6h.
In the present invention, the biomass material, sodium chlorite, glacial acetic acid and the method for water mixing are preferably by biomass
Raw material is added to the water, and then adds the glacial acetic acid of 1/5 sodium nitrite and 1/5, heats 1~2h, repeat to be added sodium nitrite,
Glacial acetic acid and the step 4 of heating time；The temperature of the heating is to remove the temperature of lignin.
Further preferably include successively being separated by solid-liquid separation and washing after removing lignin, obtains the biomass material of removing lignin.
The present invention is not particularly limited the method for separation of solid and liquid, selects separation of solid and liquid well known to those skilled in the art
Method.In the present invention, it is preferred to filter.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art, will consolidate
Solid matter after liquid separation is washed to neutrality.
After obtaining the biomass material of removing lignin, the present invention will remove the biomass material and 2wt% of lignin
Potassium hydroxide solution infiltrates row alkali process, the biomass material after obtaining alkali process.
In the present invention, the temperature of the alkali process is preferably 85~95 DEG C, and more preferably 90 DEG C；The alkali process when
Between preferably 2~3h, more preferably 2h.
The present invention is not particularly limited the biomass material of the removing lignin and the dosage of potassium hydroxide solution, selects
With dosage well known to those skilled in the art.
It in the present invention, further preferably include successively being separated by solid-liquid separation and washing, the life after obtaining alkali process after the alkali process
Raw material of substance.
The present invention is not particularly limited the method for separation of solid and liquid, selects separation method well known to those skilled in the art i.e.
It can.In the present invention, it is preferred to filter.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art, will consolidate
Solid matter after liquid separation is washed to neutrality.
After biomass material after obtaining alkali process, the present invention is by biomass material, sodium chlorite, the ice vinegar after alkali process
Acid and water mixing remove lignin again, obtain holocellulose；
In the present invention, the 2g:0.7 of the biomass material after the alkali process, sodium chlorite, glacial acetic acid and water~
0.8g:0.5mL:65mL, more preferably 2g:0.75g:0.5mL:65mL.
In the present invention, the temperature for removing lignin again is preferably 70~80 DEG C, and more preferably 75 DEG C；It is described again
The time of secondary removing lignin is preferably 1~2h.
It in the present invention, further preferably include successively being separated by solid-liquid separation and washing after the lignin of removing again.
The present invention is not particularly limited the method for separation of solid and liquid, selects separation method well known to those skilled in the art i.e.
It can.In the present invention, it is preferred to filter.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art, will consolidate
Solid matter after liquid separation is washed to neutrality.
After obtaining holocellulose, the present invention preferably mixes holocellulose at alkali again with the potassium hydroxide solution of 5wt%
Reason, obtains purifying cellulose.
In the present invention, the dosage of the holocellulose and potassium hydroxide solution is not particularly limited, and selects this field skill
Dosage known to art personnel.
In the present invention, the temperature of the alkali process again is preferably 85~95 DEG C, and more preferably 90 DEG C.
In the present invention, further preferably successively include being separated by solid-liquid separation and washing after the alkali process again, obtain at alkali again
Biomass material after reason.
The present invention is not particularly limited the method for separation of solid and liquid, selects separation method well known to those skilled in the art i.e.
It can.In the present invention, it is preferred to filter.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art, will consolidate
Solid matter after liquid separation is washed to neutrality.
After obtaining purifying cellulose, purifying cellulose is mixed the sour processing of progress by the present invention with the hydrochloric acid solution of 1wt%, is obtained
To loose purifying cellulose.
The present invention is not particularly limited the dosage of purifying cellulose and hydrochloric acid solution, selects those skilled in the art known
Dosage.
In the present invention, the temperature of the acid processing is preferably 75~85 DEG C, and more preferably 80 DEG C；The acidification
Time is preferably 2~3h.
In the present invention, further preferably successively obtaining mass concentration including separation of solid and liquid and washing after acid processing is 92~95%
Purifying cellulose.
The present invention is not particularly limited the method for separation of solid and liquid, selects separation method well known to those skilled in the art i.e.
It can.In the present invention, it is preferred to filter.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art, will consolidate
Solid matter after liquid separation is washed to neutrality.
In the present invention, the fibre of concentration needed for the purifying cellulose deployment cost application for being 5~8% by the mass concentration
Plain aqueous suspension is tieed up, the concentration of the cellulose aqueous suspension is preferably 0.2~1%, and more preferably 0.5%.
In the present invention, the biomass cellulose aqueous suspension is preferably the cleaning cellulose for being 5~8% by mass concentration
Element successively carries out ultrasonic treatment after mixing with water and high pressure homogenization handles to obtain.
In the present invention, the power of the ultrasonic treatment is preferably 700~1000W, more preferably 800~900W；It is described
The time of ultrasonic treatment is preferably 15~30min, more preferably 20min.
In the present invention, the first class pressure of the high pressure homogenization processing is preferably 80~100bar, more preferably 90~
95bar。
In the present invention, the secondary pressure of the high pressure homogenization processing is preferably 350~450bar, more preferably 400~
430bar。
In the present invention, the time of the high pressure homogenization processing is preferably 15~30min, more preferably 20~25min.
In the present invention, the aperture of filter membrane is preferably 0.22~0.45 μm when the suction filtration, and more preferably 0.45 μm.
The present invention is not particularly limited the method for suction filtration, selects suction filtration method well known to those skilled in the art.
After obtaining biomass fiber hydrogel, the present invention by obtained biomass fiber hydrogel immerse ethyl alcohol according to
It is secondary replaced, demoulding and first dry, obtain biomass cellulose paper.
In the present invention, the concentration of the ethyl alcohol is preferably 90~99.9%, and more preferably 99.7%.
The present invention is not particularly limited the dosage of ethyl alcohol, can cross and submerge biomass fiber hydrogel.
In the present invention, the displaced temperature is preferably room temperature；The displaced time is preferably 8~14h, more preferably
For 12h.
In the present invention, the filter membrane after demoulding is preferably folded in glass plate by first drying, is being dried in vacuo
It is dried in case.In the present invention, the described first dry temperature is preferably 50~70 DEG C, and more preferably 60~65 DEG C；Institute
Stating for the first dry time is preferably 2~5h, more preferably 2h.
After obtaining biomass cellulose paper, obtained biomass cellulose paper is impregnated postposition in PMMA solution by the present invention
It is dry in carrying out second on silicon wafer, obtain biomass cellulose laminated film.
In the present invention, the concentration of the PMMA solution is preferably 20~30%, and more preferably 20%.
In the present invention, the time of the dipping be preferably 12~for 24 hours, more preferably 16~20h.
The present invention is not particularly limited the dosage of PMMA solution, can submerge biomass cellulose paper.
Cellulose paper after dipping is placed on silicon wafer by the present invention to carry out second dry, and the present invention is by the cellulose after dipping
Paper is placed in the dry flatness that can be improved laminated film on silicon wafer.
In the present invention, the described second dry temperature is preferably room temperature.
After obtaining biomass cellulose laminated film, the present invention by obtained biomass cellulose laminated film by etc. from
Daughter cleaning, the biomass cellulose laminated film that obtains that treated.
In the present invention, the plasma clean carries out preferably in plasma washing machine, and the plasma is clear
The frequency 40KHZ of washing machine, power 600W, processing time are 3min.
The present invention is by carrying out plasma cleaning to biomass cellulose laminated film, in biomass cellulose laminated film
Plasma and fold are stamped on one side, are easy to load upper metal nanometer line.
Obtain that treated biomass cellulose laminated film, the place that silver nanowires dispersant liquid drop is coated by the present invention
The one side of laminated film after reason obtains biomass nano cellulose conductive composite film.
In the present invention, the mass concentration of the middle silver nanowires dispersion liquid is preferably 5~8mg/mL, more preferably 5mg/
mL。
In the present invention, the load capacity of the silver nanowires of the biomass cellulose laminated film be preferably 0.01~
0.2mg/cm2。
In the present invention, silver nanowires is calculated according to loading requirement of the biomass cellulose laminated film to silver nanowires
The specific dosage of dispersion liquid.
It in the present invention, further preferably include that the biology cellulose film drying after drop coating is obtained into biology after the drop coating
Matter nano-cellulose conductive composite film.
In the present invention, the temperature of the drying is preferably room temperature, and the present invention is not particularly limited dry method, choosing
With drying means well known to those skilled in the art.
It is described the present invention also provides the biomass nano cellulose conductive composite film that above-mentioned preparation method is prepared
The silver nanowires load capacity of laminated film is 0.01~0.2mg/cm2, the laminated film with a thickness of 0.06~0.1mm.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) cellulose is extracted from biological material
(1) 4g poplar wood powder is added in 130mL distilled water, and 1.34g sodium chlorite is added, and 1mL glacial acetic acid is added, and use is close
Envelope covers conical flask, heats 1 hour in 75 DEG C of waters bath with thermostatic control, repeats " 1.34g sodium nitrite, the sealing of 1mL glacial acetic acid to be added
The upper conical bottle of pkt. flap heats 1 hour in 75 DEG C of waters bath with thermostatic control " process 4 times, filter, cleaning sample to neutrality, obtain removing wood
The poplar wood powder of quality.
(2) the poplar wood powder for claiming 2.4 potassium hydroxide of system to be prepared into the potassium hydroxide solution and removing lignin of 2wt% is placed in
2h is heated in 90 DEG C of waters bath with thermostatic control, is filtered, cleaning sample to neutrality, the Poplar Powder after obtaining alkali process.
(3) 1.34g sodium chlorite is added into the Poplar Powder after alkali process, 1mL glacial acetic acid is placed in 75 DEG C of waters bath with thermostatic control
1h is heated, is filtered, cleaning sample to neutrality obtains holocellulose.
(4) solution of holocellulose and 5wt% potassium hydroxide is mixed, obtained mixed liquor is placed directly within 90 DEG C of constant temperature
2h is heated in water-bath, is filtered, and cleaning sample to neutrality obtains purifying cellulose.
(5) hydrochloric acid solution that 1wt% is added in purifying cellulose is placed in 80 DEG C of waters bath with thermostatic control and heats 2h, filtered, cleaning
To neutrality, loose purifying cellulose is obtained.
2) loose purifying cellulose and water are mixedly configured into the aqueous suspension of 0.2wt% concentration, and aqueous suspension is carried out
High strength supersonic processing, power 800w handle time 20min, then carry out high pressure homogenization processing, handle time 20min, level-one
80~100bar of pressure, secondary pressure arrive the aqueous suspension of finely dispersed biomass cellulose for 350~450bar,
Its pictorial diagram and TEM figure are as depicted in figs. 1 and 2 respectively, and cellulose is uniformly dispersed and is in that micro- indigo plant is translucent.By above-mentioned biomass
The aqueous suspension of cellulose takes 10mL, is filtered with 250mL glass sand core funnel and 0.45 μm of aperture filter membrane, and the suction filtration time is 30s,
It obtains with a thickness of 0.5mm, diameter is the biomass fiber hydrogel of 40mm.
3) biomass fiber hydrogel is put into ethanol solution and is replaced, the cellulose alcogel after falling off is folded in
Glass plate covering, the dry 2h in 60 DEG C of vacuum drying oven, obtains translucent flexible biomass cellulose paper, in kind
Figure is as shown in Figure 3.
4) obtained biomass cellulose paper is put into the beaker for filling the PMMA solution of the 10wt% of 30mL and impregnates 12h
Afterwards, it takes out and obtains transparent biomass cellulose laminated film after covering culture dish drying at room temperature 2h on the single throwing silicon wafer of placement,
Pictorial diagram is as shown in figure 4, as shown in Figure 4, the transparency is good.
5) biomass cellulose laminated film is put into plasma washing machine and carries out corona treatment, frequency
40KHZ, power 600W, processing time are the 3min biomass cellulose laminated film that obtains that treated.
6) silver nanowires that drop coating 28.5mL mass concentration is 5mg/mL on cellulose laminated film after treatment is dispersed
Liquid, the load capacity 0.01mg/cm of the cellophane that makes that treated to nano silver2, it is dry, it obtains flexible and transparent biomass and receives
Rice cellulose conductive composite film.Its pictorial diagram is as shown in figure 5, as shown in Figure 5, the transparency is good.
In circuit by the connection of biomass nano cellulose conductive composite film, as shown in fig. 6, small bulbs are bright, it was demonstrated that its
Electric conductivity is good, tests by four-point probe, and resistance is 6 Ω/cm.
Embodiment 2
1) biomass fiber hydrogel obtained in embodiment 1 is put into displacement 12h in ethanol solution and obtains Nanowire
Plain alcogel is tieed up, alcogel is folded in glass plate covering, dry 2h, it is fine to obtain biomass in 60 DEG C of vacuum drying oven
Tie up plain nanometer paper.
2) obtained biomass cellulose paper is put into the beaker for filling the PMMA solution of the 20wt% of 40mL and is impregnated for 24 hours
Afterwards, it takes out to place and covers culture dish drying at room temperature 3h on single throwing silicon wafer, obtain transparent biomass cellulose laminated film.
3) biomass cellulose laminated film is put into plasma washing machine and carries out corona treatment, frequency
40KHZ, power 600W, processing time are the 3min biomass nano cellulose laminated film that obtains that treated.
4) on biomass cellulose laminated film after treatment 125mL drop coating 5mg/mL silver nanowires dispersion liquid, make
The silver carrying amount of treated biomass cellulose film is 0.05mg/cm2, it is conductive to obtain flexible and transparent biomass nano cellulose
Laminated film.
Embodiment 3
1) biomass fiber hydrogel obtained in embodiment 1 is put into displacement 12h in ethanol solution and obtains cellulose
Alcogel is folded in glass plate covering by alcogel, and dry 2h, obtains biomass cellulose in 60 DEG C of vacuum drying oven
Paper.
2) obtained biomass cellulose paper is put into the beaker for filling the PMMA solution of the 20wt% of 40~50mL and is soaked
Stain for 24 hours after, take out and place single throw and covers culture dish drying at room temperature 3h on silicon wafer, obtain transparent biomass cellulose THIN COMPOSITE
Film.
3) biomass cellulose laminated film is put into plasma washing machine and carries out corona treatment, frequency
40KHZ, power 600W, processing time are the 3min biomass cellulose laminated film that obtains that treated.
4) on biomass cellulose laminated film after treatment 250mL drop coating 5mg/mL silver nanowires dispersion liquid, make
Treated, and the thin silver carrying amount of biomass cellulose is 0.1mg/cm2, obtain flexible biological matter nano-cellulose conduction THIN COMPOSITE
Film.
Embodiment 4
1) biomass fiber hydrogel obtained in embodiment 1 is put into displacement 12h in ethanol solution and obtains cellulose
Alcogel is folded in glass plate covering by alcogel, and dry 2h, obtains biomass cellulose in 60 DEG C of vacuum drying oven
Paper.
2) obtained biomass cellulose paper is put into the beaker for filling the PMMA solution of the 20wt% of 50mL and is impregnated for 24 hours
Afterwards, it takes out to place and covers culture dish drying at room temperature 3h on single throwing silicon wafer, obtain transparent biomass cellulose laminated film.
3) biomass cellulose laminated film is put into plasma washing machine and carries out corona treatment, frequency
40KHZ, power 600W, processing time are the 3min biomass cellulose laminated film that obtains that treated.
4) on biomass cellulose laminated film after treatment 610mL drop coating 5mg/mL silver nanowires dispersion liquid, make
The silver carrying amount of treated biomass cellulose film is 0.2mg/cm2, it is compound to obtain flexible biological matter nano-cellulose conduction
Film.
Fig. 7 is the light transmission curve of different silver nanowires load factors in 1~embodiment of embodiment 4；From top to bottom successively
It is 0.01mg/cm for silver carrying amount2、0.05mg/cm2、0.1mg/cm2And 0.2mg/cm2.As shown in Figure 7, as silver nanowires is negative
The raising of load rate, the resistance of conductive composite film gradually decrease (6.0~0.1 × 103 Ω/cm), and light transmittance is gradually lowered
(transmitance is 86~32% at 600nm wavelength).
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of biomass nano cellulose conductive composite film, comprising the following steps:
1) biomass cellulose aqueous suspension is filtered, obtains biomass fiber hydrogel filter membrane；The biomass cellulose
Hydrogel with a thickness of 0.5~1mm；
2) biomass fiber hydrogel that step 1) obtains is immersed in ethyl alcohol successively replaced, demoulding and first dry,
Obtain biomass cellulose paper；
3) the biomass cellulose paper that step 2) obtains is impregnated to be placed on silicon wafer in PMMA solution and carries out the second drying, obtained
To biomass cellulose laminated film；
4) the biomass cellulose laminated film for obtaining step 3) passes through plasma clean, and obtaining that treated, biomass is fine
Tie up plain laminated film；
5) silver nanowires dispersant liquid drop is coated onto the one side of step 4) the biomass cellulose laminated film that obtains that treated, is obtained
To biomass nano cellulose conductive composite film.
2. preparation method according to claim 1, which is characterized in that biomass cellulose aqueous suspension in the step 1)
Mass concentration be 0.2~1%.
3. preparation method according to claim 1, which is characterized in that the temperature replaced in the step 2) is room temperature, is set
The time changed is 8~14h.
4. preparation method according to claim 1, which is characterized in that dry temperature is 50~70 in the step 3)
DEG C, the dry time is 2h.
5. preparation method according to claim 1, which is characterized in that the mass concentration of PMMA solution is in the step 3)
20~30%.
6. preparation method according to claim 1, which is characterized in that the time impregnated in the step 3) is 12~for 24 hours.
7. preparation method according to claim 1, which is characterized in that step 4) the plasma cleaning is in plasma
It is carried out in body cleaning machine, the frequency 40KHZ of the plasma washing machine, power 600W, the processing time is 3min.
8. preparation method according to claim 1, which is characterized in that the quality of silver nanowires dispersion liquid in the step 5)
Concentration is 5~8mg/mL.
9. preparation method according to claim 1, which is characterized in that biomass cellulose laminated film in the step 5)
Silver nanowires load capacity be 0.01~0.2mg/cm2。
10. the biomass nano cellulose conduction THIN COMPOSITE that preparation method described in any one of claim 1 to 9 is prepared
Film, which is characterized in that the silver nanowires load capacity of the laminated film is 0.01~0.2mg/cm2, the thickness of the laminated film
Degree is 0.06~0.10mm.
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| CN103440907A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院青岛生物能源与过程研究所 | Cellulose nanofibers and silver nanowires composite conductive film and preparation method of composite conductive film |
| CN104867621A (en) * | 2015-04-28 | 2015-08-26 | 上海大学 | Preparation method of nano cellulose/silver nanowire composite flexible transparent conductive paper |
| CN107525832A (en) * | 2017-08-29 | 2017-12-29 | 浙江理工大学 | A kind of preparation method of the flexible fiber sensor electrode of nano silver wire modification |
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| CN103440907A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院青岛生物能源与过程研究所 | Cellulose nanofibers and silver nanowires composite conductive film and preparation method of composite conductive film |
| CN104867621A (en) * | 2015-04-28 | 2015-08-26 | 上海大学 | Preparation method of nano cellulose/silver nanowire composite flexible transparent conductive paper |
| CN107525832A (en) * | 2017-08-29 | 2017-12-29 | 浙江理工大学 | A kind of preparation method of the flexible fiber sensor electrode of nano silver wire modification |
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