CN109081932B - Preparation method and product of high-stability flexible transparent conductive cellulose membrane - Google Patents
Preparation method and product of high-stability flexible transparent conductive cellulose membrane Download PDFInfo
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- CN109081932B CN109081932B CN201810684113.6A CN201810684113A CN109081932B CN 109081932 B CN109081932 B CN 109081932B CN 201810684113 A CN201810684113 A CN 201810684113A CN 109081932 B CN109081932 B CN 109081932B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0806—Silver
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Abstract
The invention provides a preparation method and a product of a high-stability flexible transparent conductive cellulose membrane, wherein the method comprises the following steps: dissolving cellulose pulp in a cellulose solvent, and preparing a regenerated cellulose membrane through regeneration treatment; preparing a starch solution; dispersing silver nanowires in a starch solution to form a silver nanowire-starch solution, and covering the silver nanowire-starch solution on a cellulose membrane to obtain a sample; and drying the prepared sample in an oven to obtain the high-stability flexible transparent conductive cellulose film. According to the invention, the effective adhesion of the silver nanowires on the cellulose membrane substrate is realized by introducing the starch buffer layer, so that the conductive stability and the friction resistance of the conductive film are greatly increased, and the high-end quality of the flexible transparent conductive film is improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a preparation method of a high-stability flexible transparent conductive cellulose membrane and a product.
[ background of the invention ]
With the progress of modern technologies, the flexibility, foldability and wearability of electronic devices have become the development trend of future electronic technologies. Compared with the traditional electronic device, the flexible electronic equipment has good application prospect in the fields of communication, information, biomedicine, mechanical manufacturing, aerospace, national defense safety and the like due to the unique flexibility and ductility of the flexible electronic equipment. The flexible transparent conductive film is a prerequisite basis for the preparation of flexible electronic devices, and therefore, needs to have unique properties including light weight, deformability, nonfriability, good conductivity, high optical transparency, good mechanical properties, high thermal and chemical stability, and the like.
Common substrates of transparent conductive films include high polymer transparent films such as polyethylene terephthalate (PET) films and Polycarbonate (PC), and the films have the characteristics of light weight, ultrathin property, good flexibility and the like. However, these high molecular weight organic polymers also present their own disadvantages. For example, the high polymers have low light transmittance at high temperature, are easy to deform at high temperature, have high heat shrinkage, are difficult to degrade, are easy to form white garbage, can seriously damage the ecological environment and threaten the survival of human beings.
In order to realize sustainable development of resources, the need to replace fossil raw materials with new materials has been urgent. The cellulose is used as a cheap natural polymer material, has the advantages of wide source range, degradability, regeneration and the like, the prepared transparent flexible cellulose membrane is more and more widely concerned, and the huge natural reserve can completely meet the requirements of electronic products on conductive films.
The conductive film formed by the metal nanowires has high light transmittance, low resistivity and excellent thermal, mechanical and chemical stability. In addition, the silver nanowires have good electrical and thermal conductivity and ductility, and are therefore particularly suitable for preparing transparent flexible conductive films. However, the silver nanowires belong to inorganic metals, the cellulose membrane substrate is an organic high molecular polymer, the effective combination between the silver nanowire conducting layer and the cellulose membrane substrate can be seriously limited due to the incompatibility of the silver nanowires and the cellulose membrane substrate, and the conducting layer of the formed flexible transparent conducting film is easy to fall off from the flexible substrate, so that the great reduction and extreme instability of the conducting performance are induced. Therefore, how to improve the effective combination between the silver nanowire conducting layer and the cellulose membrane substrate becomes a research hotspot of the silver nanowire-based flexible transparent cellulose conducting film, and the research significance of improving the quality of the flexible transparent conducting film is provided.
Typically, silver nanowires are dispersed in water or an organic solution and then spin coated onto a cellulose film substrate. The attachment of the silver nanowires on the cellulose film is achieved by evaporation/volatilization of moisture or organic solvent. However, the silver nanowires are inorganic metals, the cellulose membrane is an organic high molecular polymer, and the silver nanowires and the cellulose membrane are incompatible and cannot be firmly combined, so that the silver nanowire conducting layer is easy to fall off from the cellulose membrane substrate, and the conducting performance of the conducting membrane is greatly fluctuated.
[ summary of the invention ]
One of the technical problems to be solved by the present invention is to provide a method for preparing a high-stability flexible transparent conductive cellulose film, which is to introduce a starch buffer layer to realize effective adhesion of silver nanowires on a cellulose film substrate, thereby greatly increasing the conductive stability and the friction resistance of the conductive film and improving the high-end quality of the flexible transparent conductive film.
The present invention achieves one of the above technical problems:
a preparation method of a flexible transparent conductive cellulose membrane with high stability comprises the following steps:
(1) dissolving cellulose pulp in a cellulose solvent, and preparing a regenerated cellulose membrane through regeneration treatment;
(2) preparing a starch solution;
(3) dispersing silver nanowires in a starch solution to form a silver nanowire-starch solution, and covering the silver nanowire-starch solution on a cellulose membrane to obtain a sample;
(4) and drying the prepared sample in an oven to obtain the high-stability flexible transparent conductive cellulose film.
Further, the cellulose pulp in the step (1) is wood dissolving pulp, non-wood dissolving pulp or cotton.
Further, the cellulose solvent in the step (1) is one of ionic liquid, N-methylmorpholine-N-oxide, DMAC-LiCl and NaOH-urea.
Further, in the step (2), the starch solution is corn starch, sweet potato starch or modified starch.
Further, the concentration of the starch solution in the step (2) is less than 10 g/L.
Further, the covering mode in the step (3) includes spin coating by a spin coater, spin coating by a coater, or centrifugal mode by a centrifuge.
Further, the treatment temperature of the oven in the step (4) is 40-120 ℃, and the treatment time is 20-120 min.
The second technical problem to be solved by the present invention is to provide a high-stability flexible transparent conductive cellulose film, i.e. by introducing a starch buffer layer, effective adhesion of silver nanowires on a cellulose film substrate is realized, thereby greatly increasing the conductive stability and the friction resistance of the conductive film, and improving the high-end quality of the flexible transparent conductive film.
The invention realizes the second technical problem in the following way:
a high-stability flexible transparent conductive cellulose film prepared by the method comprising:
(1) dissolving cellulose pulp in a cellulose solvent, and preparing a regenerated cellulose membrane through regeneration treatment;
(2) preparing a starch solution;
(3) dispersing silver nanowires in a starch solution to form a silver nanowire-starch solution, and covering the silver nanowire-starch solution on a cellulose membrane to obtain a sample;
(4) and drying the prepared sample in an oven to obtain the high-stability flexible transparent conductive cellulose film.
Further, the cellulose pulp in the step (1) is wood dissolving pulp, non-wood dissolving pulp or cotton;
in the step (1), the cellulose solvent is one of ionic liquid, N-methylmorpholine-N-oxide, DMAC-LiCl and NaOH-urea;
in the step (2), the starch solution is corn starch, sweet potato starch or modified starch, and the concentration of the starch solution is less than 10 g/L.
Further, the covering mode in the step (3) is spin coating by a spin coater, spin coating by a coater or centrifugal by a centrifuge;
the processing temperature of the oven in the step (4) is 40-120 ℃, and the processing time is 20-120 min.
The invention has the following advantages:
according to the invention, the silver nanowires are dispersed in the starch solution, and the starch buffer layer is introduced, so that on one hand, starch and cellulose are isomeric substances, organic fusion can exist between the starch and the cellulose, and on the other hand, the starch solution can semi-wrap the silver nanowires and firmly adhere the silver nanowires to the surface of the cellulose membrane, so that organic combination of the silver nanowires and the cellulose membrane is realized, the conductive stability and the friction resistance of the conductive membrane are greatly increased, and the high-end quality of the flexible transparent conductive membrane is finally improved.
[ detailed description ] embodiments
The invention relates to a preparation method of a high-stability flexible transparent conductive cellulose membrane, which comprises the following steps:
(1) dissolving cellulose pulp in a cellulose solvent, and preparing a regenerated cellulose membrane through regeneration treatment;
(2) preparing a starch solution;
(3) dispersing silver nanowires in a starch solution to form a silver nanowire-starch solution, and covering the silver nanowire-starch solution on a cellulose membrane to obtain a sample;
(4) and drying the prepared sample in an oven to obtain the high-stability flexible transparent conductive cellulose film.
The cellulose pulp in the step (1) is wood dissolving pulp, non-wood dissolving pulp or cotton.
In the step (1), the cellulose solvent is one of ionic liquid, N-methylmorpholine-N-oxide, DMAC-LiCl and NaOH-urea.
In the step (2), the starch solution is corn starch, sweet potato starch or modified starch.
The concentration of the starch solution in the step (2) is less than 10 g/L.
The covering mode in the step (3) is spin coating of a spin coater, spin coating of a coater or centrifugal mode of a centrifugal machine.
The processing temperature of the oven in the step (4) is 40-120 ℃, and the processing time is 20-120 min.
The invention also relates to a high-stability flexible transparent conductive cellulose membrane prepared by the preparation method.
The present invention will be further described with reference to the following examples.
Example 1: preparation of high-stability flexible transparent conductive cellulose membrane
And (1) dissolving broadleaf wood dissolving pulp in ionic liquid, and preparing a regenerated cellulose membrane through regeneration.
And (2) preparing corn starch and preparing a starch solution of 5 g/L.
Step (3), dissolving the silver nanowires in a starch solution to prepare a silver nanowire-starch solution with the concentration of 50 ppm; and spin-coating the silver nanowire-starch solution on the cellulose membrane by using a spin coater to obtain a sample.
And (4) putting the sample obtained in the step (3) into an oven at 80 ℃ and treating for 40 min.
After 100 times of sticking by using the 3M adhesive tape in the step (5), the conductivity of the conductive cellulose film is only increased from 30 omega/□ to 38 omega/□, and the transparency is 75%.
Example 2: preparation of high-stability flexible transparent conductive cellulose membrane
And (1) dissolving the softwood dissolving pulp in an N-methylmorpholine-N-oxide solution, and preparing a regenerated cellulose membrane through regeneration.
And (2) preparing oxidized starch and preparing 8g/L starch solution.
Step (3), dissolving the silver nanowires in a starch solution to prepare a silver nanowire-starch solution with the concentration of 100 ppm; and spin-coating the silver nanowire-starch solution on the cellulose membrane by using a coater to obtain a sample.
And (4) putting the sample obtained in the step (3) into an oven at 50 ℃ and treating for 80 min.
After 200 times of pasting with 3M adhesive tape in the step (5), the conductivity of the conductive cellulose film is only increased from 10 omega/□ to 20 omega/□, and the transparency is 70%.
Example 3: preparation of high-stability flexible transparent conductive cellulose membrane
Step (1), preparing cotton to be dissolved in DMAC-LiCl, and preparing a regenerated cellulose membrane through regeneration.
And (2) preparing sweet potato starch and preparing 2g/L starch solution.
Step (3), dissolving the silver nanowires in a starch solution to prepare a silver nanowire-starch solution with the concentration of 20 ppm; and centrifuging the silver nanowire-starch solution onto the cellulose membrane by using a centrifuge to obtain a sample.
And (4) putting the sample obtained in the step (3) into an oven at 100 ℃ and treating for 30 min.
After 50 times of wiping by using an eraser, the conductivity of the conductive cellulose membrane is still maintained at 80 omega/□, and the transparency is 80%.
Example 4: preparation of high-stability flexible transparent conductive cellulose membrane
And (1) dissolving bamboo dissolving pulp in NaOH-urea, and preparing a regenerated cellulose membrane through regeneration.
And (2) preparing corn starch and preparing a starch solution of 4 g/L.
Step (3), dissolving the silver nanowires in a starch solution to prepare a silver nanowire-starch solution with the concentration of 80 ppm; and centrifuging the silver nanowire-starch solution onto the cellulose membrane by using a centrifuge to obtain a sample.
And (4) putting the sample obtained in the step (3) into an oven at 50 ℃ and treating for 120 min.
After 100 times of wiping by using an eraser in the step (5), the conductivity of the conductive cellulose film is only increased from 15 omega/□ to 22 omega/□, and the transparency is 72 percent.
According to the invention, the silver nanowires are dispersed in the starch solution, and the starch buffer layer is introduced, so that on one hand, starch and cellulose are isomeric substances, organic fusion can exist between the starch and the cellulose, and on the other hand, the starch solution can semi-wrap the silver nanowires and firmly adhere the silver nanowires to the surface of the cellulose membrane, so that organic combination of the silver nanowires and the cellulose membrane is realized, the conductive stability and the friction resistance of the conductive membrane are greatly increased, and the high-end quality of the flexible transparent conductive membrane is finally improved.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (9)
1. A preparation method of a high-stability flexible transparent conductive cellulose membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving cellulose pulp in a cellulose solvent, and preparing a regenerated cellulose membrane through regeneration treatment;
(2) preparing a starch solution; in the step (2), the starch solution is corn starch, sweet potato starch or modified starch;
(3) dispersing silver nanowires in a starch solution to form a silver nanowire-starch solution, and covering the silver nanowire-starch solution on a cellulose membrane to obtain a sample;
(4) and drying the prepared sample in an oven to obtain the high-stability flexible transparent conductive cellulose film.
2. The method for preparing a flexible transparent conductive cellulose film with high stability according to claim 1, wherein: the cellulose pulp in the step (1) is wood dissolving pulp, non-wood dissolving pulp or cotton.
3. The method for preparing a flexible transparent conductive cellulose film with high stability according to claim 1, wherein: in the step (1), the cellulose solvent is one of ionic liquid, N-methylmorpholine-N-oxide, DMAC-LiCl and NaOH-urea.
4. The method for preparing a flexible transparent conductive cellulose film with high stability according to claim 1, wherein: the concentration of the starch solution in the step (2) is less than 10 g/L.
5. The method for preparing a flexible transparent conductive cellulose film with high stability according to claim 1, wherein: the covering mode in the step (3) is spin coating of a spin coater, spin coating of a coater or centrifugal mode of a centrifugal machine.
6. The method for preparing a flexible transparent conductive cellulose film with high stability according to claim 1, wherein: the processing temperature of the oven in the step (4) is 40-120 ℃, and the processing time is 20-120 min.
7. A flexible transparent conductive cellulose membrane of high stability which characterized in that: the high-stability flexible transparent conductive cellulose film is prepared based on the preparation method of the high-stability flexible transparent conductive cellulose film in claim 1.
8. A high stability flexible transparent conductive cellulose film according to claim 7, wherein: the cellulose pulp in the step (1) is wood dissolving pulp, non-wood dissolving pulp or cotton;
in the step (1), the cellulose solvent is one of ionic liquid, N-methylmorpholine-N-oxide, DMAC-LiCl and NaOH-urea;
in the step (2), the starch solution is corn starch, sweet potato starch or modified starch, and the concentration of the starch solution is less than 10 g/L.
9. A high stability flexible transparent conductive cellulose film according to claim 7, wherein: the covering mode in the step (3) is spin coating of a spin coater, spin coating of a coater or centrifugal mode of a centrifugal machine;
the processing temperature of the oven in the step (4) is 40-120 ℃, and the processing time is 20-120 min.
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| CN110299221A (en) * | 2019-06-25 | 2019-10-01 | 武汉工程大学 | A kind of composite and flexible transparent conductive film and preparation method thereof |
| CN111019180A (en) * | 2019-11-27 | 2020-04-17 | 福建农林大学 | Preparation method of green environment-friendly transparent conductive cellulose membrane and product thereof |
| CN111171162B (en) * | 2020-01-13 | 2020-12-04 | 福建农林大学 | Cellulose electron transport polymer and preparation method and application thereof |
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| CN107955198A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院大连化学物理研究所 | A kind of preparation method of nano-silver thread-chitosan self assembly conductive film coating |
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