CN113096885B - Preparation method of low-resistance high-transparency conductive film - Google Patents
Preparation method of low-resistance high-transparency conductive film Download PDFInfo
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Abstract
The invention relates to a conductive material technology, in particular to a preparation method of a low-resistance high-transparency conductive film. The conductive film prepared from carboxymethyl hemicellulose and graphene has excellent toughness, conductivity and visible light transmittance, high density and excellent mechanical property, the conductivity of the conductive film is not obviously attenuated after the conductive film is bent for many times, the conductive film can be repeatedly utilized, and the cost is obviously reduced.
Description
Technical Field
The invention relates to a conductive material technology, in particular to a preparation process of a conductive film, and specifically relates to a preparation method of a low-resistance high-transparency conductive film.
Background
The conductive film is a film having a conductive function, and the high-transparency conductive film is a film which can conduct electricity and has a high transparency in a visible light range, and mainly includes a metal film system, an oxide film system, other compound film systems, a polymer film system, a composite film system, and the like. The conductive film has wide application in the fields of flat-panel televisions, touch screens, intelligent window glass, light-emitting diodes, photovoltaic cells and the like. In transparent conductive films, relatively widely applied current Indium Tin Oxide (Indium-Tin Oxide) transparent conductive film glass (ITO film), Philips corporation prepared a low resistivity ITO film on a glass substrate by using Indium acetate and Tin chloride precursors through a spray pyrolysis method as early as 1968, and after decades of research and application, the ITO film gradually became the material with the best practical comprehensive performance and the widest application range among transparent conductive film materials, and was widely applied to numerous industries such as flat panel displays, Light Emitting diodes (Light Emitting diodes), thin film transistors, heat mirrors, electrochromic devices, and the like, and showed great application potential in military fields such as electromagnetic shielding windows, radar waves, infrared stealths, and the like. However, as the thickness of the ITO thin film increases, the cost thereof increases sharply, and the transparency thereof decreases sharply, and in order to solve the dependence on the ITO thin film, a great deal of research and development and popularization of other highly transparent conductive thin films are performed.
The Chinese patent with the prior art granted publication number of CN109686477B discloses a high-temperature resistant composite transparent conductive film and a preparation method thereof, wherein the composite transparent conductive film is of a layered structure, and specifically, an ion blocking layer (1), a buffer layer (2), an inner metal protection layer (3), a metal layer (4), an outer metal protection layer (5) and a functional layer (6) are sequentially arranged on the upper surface of a transparent substrate (7) from inside to outside; the inner metal protection layer (3) and the outer metal protection layer (5) are made of Ti, Cu, Al, Ni, Nb, V, Cr, nickel-chromium-vanadium alloy, vanadium-titanium alloy, aluminum-nickel alloy, nickel-chromium alloy, aluminum-vanadium alloy or copper-chromium alloy; the thickness of the inner metal protection layer (3) and the outer metal protection layer (5) is 0.2-1.5 nm; and preparing each layer on the transparent substrate by adopting a magnetron sputtering method in sequence. However, the preparation process of the scheme is complex, and the flexibility of the conductive film is insufficient.
In addition, the chinese patent with the publication number of CN104134484B discloses a flexible transparent conductive film based on nano-silver wires and a preparation method thereof, wherein the transparent conductive film comprises 1) a nano-silver wire network layer, 2) a nano-particle filling structure, and 3) an optical adhesive layer. However, the transparent conductive film manufactured by the scheme has relatively low light transmittance, and thus the application of the subsequent process is greatly influenced.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a low-resistance high-transparency conductive film, in which carboxymethyl hemicellulose and graphene are used to prepare a conductive film, the conductive film has excellent toughness, conductivity and visible light transmittance, high density and excellent mechanical properties, the conductivity of the conductive film is not significantly attenuated after being bent for many times, the conductive film can be repeatedly used, and the cost is significantly reduced.
In order to achieve the above object, the present invention provides the following technical solutions.
A preparation method of a low-resistance high-transparency conductive film comprises the following steps: and dispersing carboxymethyl hemicellulose and graphene in an alkaline urine solution, adding a cross-linking agent to prepare graphene/carboxymethyl hemicellulose gel, and performing hot-press molding to obtain the conductive film.
The preparation method of the low-resistance high-transparency conductive film specifically comprises the following steps:
s1: dispersing the dried hemicellulose into sufficient deionized water at 55-60 ℃, and adding a sodium hydroxide solution for constant-temperature alkalization reaction for at least 10 min; then adding sodium chloroacetate with the weight not less than that of the hemicellulose, heating to 65-68 ℃, adding a sodium hydroxide solution, carrying out constant-temperature etherification reaction for at least 75min, neutralizing the reaction system to be neutral by using an acetic acid solution, precipitating with absolute ethanol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl hemicellulose;
s2: preparing an alkaline urine solution containing 0.5-1.0% of carboxymethyl hemicellulose, adding graphene which accounts for 0.4-0.8% of the weight of the carboxymethyl hemicellulose, ultrasonically dispersing for at least 1h, adding a cross-linking agent, heating to 42-50 ℃, stirring at a high speed for reaction for at least 30min, standing for 2-3 h, washing with distilled water and acetone in sequence after high-speed centrifugation, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
s3: and (4) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step S2 to obtain the conductive film.
According to the method, carboxymethylation is carried out on hemicellulose through etherification, then an alkaline urine solution of the carboxymethylation solution is prepared, graphene is added to prepare gel, the alkaline urine can break the connection between graphene layers, the graphene is stripped layer by layer, the graphene layers and the carboxymethyl hemicellulose are inserted layer by layer, the carboxymethyl hemicellulose and the graphene layers can form a new hydrogen bond network, the dispersibility of the graphene is obviously improved, a stable cross-linking structure is formed under the action of a cross-linking agent, the carboxymethyl grafted by the hemicellulose further stabilizes the cross-linking degree, the conductivity of the graphene can be fully exerted, and finally the conductive film prepared by hot press molding is higher in toughness, better in conductivity, better in transparency, high in densification degree and excellent in mechanical property.
In some preferred embodiments, the weight average relative molecular mass of the hemicellulose of step S1 is 20000 to 100000, and the dispersion coefficient is 1.2 to 2.0.
In some preferred embodiments, the sodium hydroxide solution in the constant-temperature alkalization reaction in the step S1 has a mass fraction of 1-2% and is added in an amount of 3-5 times the weight of the hemicellulose.
In some preferred embodiments, the sodium hydroxide solution for the constant temperature etherification reaction in step S1 has a mass fraction of 1-2% and is added in an amount of 5-8 times the weight of hemicellulose.
In some preferred embodiments, the mass fraction of the acetic acid solution in step S1 is 2-4%.
In some preferred embodiments, the alkaline aqueous solution of step S2 is a solution of 7 parts by weight of sodium hydroxide and 12 parts by weight of urea dissolved in 81 parts by weight of distilled water.
In some preferred embodiments, the stirring rate in step S2 is 300 to 900 r/min.
In some preferred embodiments, the graphene in step S2 contains 10 to 30%, preferably 10 to 25%, more preferably 15 to 25%, and most preferably 20% of nitrogen-doped graphene.
In other preferred embodiments, the nitrogen-doped graphene in the graphene obtained in step S2 is specifically prepared by the following method: preparing a graphene dispersion liquid, adding urea according to the weight ratio of graphene to urea of 1: 5-15, carrying out hydrothermal reaction for 6-12 h at 160-180 ℃ after complete dissolution, taking out gel, carrying out heat preservation for at least 1h at 1000-1050 ℃ under high-purity argon, and naturally cooling to obtain the graphene/urea composite material. In further research, the inventor finds that the conductivity and the mechanical strength of the conductive film are improved by doping a part of nitrogen-doped graphene into common graphene oxide, and the possible reason is that the introduction of nitrogen element strengthens the association quantity and the association fastness of a hydrogen bond network, the graphene hardly has an agglomeration phenomenon, the dispersion degree is higher, and therefore the conductivity and the mechanical strength of the conductive film are further improved.
In some preferred embodiments, in step S2, cerium-doped carbon quantum dots with a weight of 0.012-0.015% of that of the carboxymethyl hemicellulose are further added into the carboxymethyl hemicellulose solution with the addition of the graphene.
In other preferred embodiments, the cerium-doped carbon quantum dots in step S2 are prepared by the following steps: dissolving cerium oxalate in sufficient 10-15% dilute hydrochloric acid solution, continuously stirring for at least 45min at 80-85 ℃ at 300-900 r/min, then adding polyethylene glycol with the weight 5-8 times of that of the cerium oxalate, continuously stirring for at least 30min to form uniform and transparent liquid, heating for at least 10min at 120-200 ℃ to obtain black blocks, dissolving the black blocks with a large amount of deionized water, centrifuging at high speed of 1500-6000 r/min, taking supernatant, dialyzing, and freeze-drying to obtain the cerium oxalate. The method prepares the cerium-doped carbon quantum dots by using cerium oxalate and polyethylene glycol, and the obtained carbon quantum dots are approximately uniform and spherical in shape, have an average size of about 2.5nm, can be uniformly dispersed in water, and have no precipitation and agglomeration; research finds that after the cerium-doped carbon quantum dots are added into the graphene conductive film in a proper amount, the conductivity of the conductive film is favorably improved, the bending resistance of the conductive film is obviously improved, the conductivity of the conductive film is not obviously attenuated after the conductive film is bent for multiple times, the conductive film can be recycled, and the cost is obviously reduced.
In some preferred embodiments, the ultrasonic frequency of the ultrasonic dispersion of step S2 is 30 to 50KHz, and the ultrasonic density is 0.3 to 0.8W/cm 2 。
In some preferred embodiments, the crosslinking agent in step S2 is one of epichlorohydrin, dicumyl peroxide or glutaraldehyde, and the amount of the crosslinking agent is 0.5-2.0% by weight of the carboxymethyl hemicellulose solution.
In some preferred embodiments, the high speed stirring rate of step S2 is 900 to 1500 r/min.
In some preferred embodiments, the high-speed centrifugation speed of step S2 is 3000-6000 r/min.
In some preferred embodiments, the hot pressing conditions of step S3 are: the temperature is 45-70 ℃, the time is 1.0-4.0 h, and the pressure is 50-80 pa.
According to the method, carboxymethyl hemicellulose is prepared through etherification reaction, then an alkaline urine solution of carboxymethyl hemicellulose is prepared, graphene is added to prepare gel, the carboxymethyl hemicellulose and the graphene form a stable cross-linking structure under the action of a cross-linking agent, the conductivity of the graphene and the cross-linking effect of the carboxymethyl hemicellulose can be fully exerted, finally, a conductive film with excellent toughness, conductivity and visible light transmittance is prepared through hot press molding, the conductive film is high in structure density and excellent in mechanical property, cerium-doped carbon quantum dots are added into the components, the conductivity and the conductive bending resistance of the conductive film are remarkably improved, the conductivity of the conductive film is not remarkably attenuated after the conductive film is bent for multiple times, the conductive film can be recycled, and the cost is remarkably reduced.
The present invention also provides a conductive film obtained by the aforementioned method.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The invention has the beneficial effects that:
carboxymethylation is carried out on hemicellulose through etherification, then an alkaline urine solution of the carboxymethylation solution is prepared, graphene is added to prepare gel, the alkaline urine can break the connection between graphene layers, the graphene is stripped layer by layer, the graphene layers and the carboxymethyl hemicellulose are inserted layer by layer, the carboxymethyl hemicellulose can also form a new hydrogen bond network with the graphene layers, the dispersibility of the graphene is obviously improved, a stable cross-linking structure is formed under the action of a cross-linking agent, the carboxymethyl grafted by the hemicellulose further stabilizes the cross-linking degree, the conductivity of the graphene can be fully exerted, and finally, the conductive film prepared by hot press molding is higher in toughness, better in conductivity, better in transparency, high in densification degree and excellent in mechanical property.
Doping a part of nitrogen-doped graphene in the graphene oxide is beneficial to improving the conductivity and mechanical strength of the conductive film, and the possible reason is that the introduction of the nitrogen element strengthens the association quantity and association fastness of a hydrogen bond network, the graphene almost has no agglomeration phenomenon, the dispersion degree of the graphene is higher, and therefore the conductivity and mechanical strength of the conductive film are further improved.
Cerium-doped carbon quantum dots are prepared from cerium oxalate and polyethylene glycol, the obtained carbon quantum dots are approximately uniform and spherical in shape, the average size is about 2.5nm, and the carbon quantum dots can be uniformly dispersed in water without precipitation and agglomeration.
After the cerium-doped carbon quantum dots are added into the graphene conductive film in a proper amount, the conductivity of the conductive film is favorably improved, the bending resistance of the conductive film is obviously improved, the conductivity of the conductive film is not obviously attenuated after the conductive film is bent for many times, the conductive film can be repeatedly utilized, and the cost is obviously reduced.
The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.
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The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a transmission electron micrograph of cerium-doped carbon quantum dots obtained in example 3 of the present invention;
fig. 2 is a schematic view of the particle size distribution of the cerium-doped carbon quantum dots obtained in example 3 of the present invention.
Detailed Description
Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated herein by reference in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5(1 to 5)" is described, the described range is understood to include ranges of "1 to 4(1 to 4)", "1 to 3(1 to 3)", "1 to 2(1 to 2) and 4 to 5(4 to 5)", "1 to 3(1 to 3) and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges, and all integers and fractions within the ranges.
When the term "about" is used to describe a numerical value or an end point value of a range, the disclosure should be understood to include the specific value or end point referred to.
Furthermore, "or" means "or" unless expressly indicated to the contrary, rather than "or" exclusively. For example, condition a "or" B "applies to any of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of the elements or components also include the plural unless it is clear that the singular forms a number.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The present invention is described in detail below.
Example 1: a low-resistance high-transparency conductive film:
the embodiment provides a low-resistance high-transparency conductive film, which is prepared by the following steps:
1): 5g of dried hemicellulose (weight average molecular weight 25000 and dispersion coefficient of 1.2) is dispersed in 200mL of 50 ℃ deionized water, and 15g of 2% sodium hydroxide solution is added for constant temperature alkalization reaction for 10 min; then adding 5g of sodium chloroacetate, heating to 68 ℃, adding 25g of 2% sodium hydroxide solution, carrying out constant temperature etherification reaction for 75min, neutralizing the reaction system to be neutral by using 2% acetic acid solution, precipitating with absolute ethyl alcohol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl hemicellulose;
2): preparing a graphene dispersion liquid, adding urea according to the weight ratio of 1:5 of graphene to urea, completely dissolving, carrying out hydrothermal reaction for 12h at 160 ℃, taking out gel, carrying out heat preservation for 1h at 1050 ℃ under high-purity argon, and naturally cooling to obtain nitrogen-doped graphene;
3): dissolving 1g of cerium oxalate in 150g of 10% dilute hydrochloric acid solution, continuously stirring for 60min at the temperature of 80 ℃ at 300r/min, then adding 5g of PEG-600, continuously stirring for 30min to form uniform and transparent liquid, heating at the temperature of 120 ℃ for 30min to obtain black blocks, dissolving with a large amount of deionized water, centrifuging at the high speed of 1500r/min for 20min, taking supernatant, dialyzing, and freeze-drying to obtain cerium-doped carbon quantum dots;
4): fully dissolving 10g of carboxymethyl hemicellulose obtained in the step 1) in 990g of an alkaline urine solution, and then adding 32mg of graphene oxide, 8mg of nitrogen-doped graphene obtained in the step 2) and 1.2mg of cerium-doped carbon quantum dots obtained in the step 3); 30KHz, 0.3W/cm 2 Ultrasonically dispersing for 2 hours, adding 5g of epoxy chloropropane, heating to 45 ℃, stirring at a high speed of 900r/min for reacting for 45 minutes, standing for 2 hours, centrifuging at a high speed of 3000r/min for 20 minutes, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
5): and (3) carrying out hot-press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step S4 at the temperature of 45 ℃, the time of 4.0h and the pressure of 50pa to obtain the low-resistance high-transparency conductive film.
Example 2: a low-resistance high-transparency conductive film:
the embodiment provides a low-resistance high-transparency conductive film, which is prepared by the following steps:
1): 5g of dried hemicellulose (weight average molecular weight 27000 and dispersion coefficient 1.5) is dispersed in 200mL of 60 ℃ deionized water, and 25g of 2% sodium hydroxide solution is added for constant-temperature alkalization reaction for 20 min; then adding 10g of sodium chloroacetate, heating to 68 ℃, adding 40g of 2% sodium hydroxide solution, carrying out constant temperature etherification reaction for 90min, neutralizing the reaction system to be neutral by using 4% acetic acid solution, precipitating with absolute ethyl alcohol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl hemicellulose;
2): preparing graphene dispersion liquid, adding urea according to the weight ratio of 1:10 of graphene to urea, completely dissolving, carrying out hydrothermal reaction at 180 ℃ for 6 hours, taking out gel, carrying out heat preservation for 2 hours under the environment of high-purity argon and 1000 ℃, and naturally cooling to obtain nitrogen-doped graphene;
3): dissolving 1g of cerium oxalate in 200g of 15% dilute hydrochloric acid solution, continuously stirring for 45min at the temperature of 85 ℃ at 900r/min, then adding 8g of PEG-1000, continuously stirring for 60min to form uniform and transparent liquid, heating at the temperature of 200 ℃ for 10min to obtain black blocks, dissolving with a large amount of deionized water, centrifuging at the high speed of 6000r/min for 5min, taking supernate, dialyzing, and freeze-drying to obtain cerium-doped carbon quantum dots;
4): fully dissolving 10g of carboxymethyl hemicellulose obtained in the step 1) in 1490g of an alkaline urine solution, and adding 64mg of graphene oxide, 16mg of nitrogen-doped graphene obtained in the step 2) and 1.5mg of cerium-doped carbon quantum dots obtained in the step 3); 50KHz, 0.8W/cm 2 Ultrasonically dispersing for 1h, adding 8g of dicumyl peroxide, heating to 50 ℃, stirring at 1500r/min at a high speed for reaction for 30min, standing for 3h, centrifuging at 6000r/min at a high speed for 5min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
5): and (3) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step 4) at the temperature of 70 ℃, the time of 4.0h and the pressure of 80pa to obtain the low-resistance high-transparency conductive film.
Example 3: a low-resistance high-transparency conductive film:
the embodiment provides a low-resistance high-transparency conductive film, which is prepared by the following steps:
1): 5g of dried hemicellulose (weight average molecular weight 27000 and dispersion coefficient of 1.5) is dispersed in 200mL of 55 ℃ deionized water, and 20g of 1.5% sodium hydroxide solution is added for constant-temperature alkalization reaction for 15 min; then adding 8g of sodium chloroacetate, heating to 66 ℃, adding 32g of 1.5% sodium hydroxide solution, carrying out constant temperature etherification reaction for 90min, neutralizing the reaction system to be neutral by using 3% acetic acid solution, precipitating with absolute ethyl alcohol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl hemicellulose;
2): preparing a graphene dispersion liquid, adding urea according to the weight ratio of 1:12 of graphene to urea, completely dissolving, carrying out hydrothermal reaction for 10h at 165 ℃, taking out gel, carrying out heat preservation for 2h under the environment of high-purity argon and 1020 ℃, and naturally cooling to obtain nitrogen-doped graphene;
3): dissolving 1g of cerium oxalate in 200g of 12% dilute hydrochloric acid solution, continuously stirring for 60min at the temperature of 84 ℃ at 600r/min, then adding 6g of PEG-800, continuously stirring for 45min to form uniform and transparent liquid, heating at the temperature of 180 ℃ for 15min to obtain a black block, dissolving with a large amount of deionized water, centrifuging at the speed of 3000r/min for 10min, taking a supernatant, dialyzing, and freeze-drying to obtain cerium-doped carbon quantum dots, wherein a lens diagram is shown in figure 1, and a particle size distribution diagram is shown in figure 2;
4): fully dissolving 10g of the carboxymethyl hemicellulose obtained in the step 1) in 1990g of an alkaline urine solution, and adding 48mg of graphene oxide, 12mg of nitrogen-doped graphene obtained in the step 2) and 1.4mg of cerium-doped carbon quantum dots obtained in the step 3); 45KHz, 0.5W/cm 2 Ultrasonically dispersing for 1.5h, adding 8g of glutaraldehyde, heating to 48 ℃, stirring at a high speed of 1200r/min for reaction for 45min, standing for 2h, centrifuging at a high speed of 4500r/min for 10min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
5): and (3) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step 4) at the temperature of 60 ℃, for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 4: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1): dispersing 5g of dried cellulose (with the weight-average molecular weight of 86000) in 200mL of 55 ℃ deionized water, adding 20g of 1.5% sodium hydroxide solution, and carrying out constant-temperature alkalization reaction for 15 min; then adding 8g of sodium chloroacetate, heating to 66 ℃, adding 32g of 1.5% sodium hydroxide solution, carrying out constant temperature etherification reaction for 90min, neutralizing the reaction system to be neutral by using 3% acetic acid solution, precipitating with absolute ethyl alcohol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl cellulose;
2): same as step 2) of example 3;
3): same as step 3 of example 3);
4): fully dissolving 10g of the carboxymethyl cellulose obtained in the step 1) in 1990g of an alkaline urine solution, adding 48mg of graphene oxide, 12mg of nitrogen-doped graphene obtained in the step 2) and 1.4mg of cerium-doped carbon quantum dots obtained in the step 3); 45KHz, 0.5W/cm 2 Ultrasonic dispersing for 1.5h, adding 8g glutaraldehyde, heating to 48 deg.C, stirring at 1200r/min for 45min, standing for 2h, and centrifuging at 4500r/minWashing with distilled water and acetone sequentially after 10min, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl cellulose gel;
5): and (3) carrying out hot-press molding on the graphene/carboxymethyl cellulose gel obtained in the step 4) at the temperature of 60 ℃, for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 5: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1): same as step 2) of example 3;
2): same as step 3 of example 3);
3): fully dispersing 10g of cellulose (with the weight-average molecular weight of 86000) in 1990g of an alkaline urine solution, adding 48mg of graphene oxide, 12mg of nitrogen-doped graphene obtained in the step 1) and 1.4mg of cerium-doped carbon quantum dots obtained in the step 2); 45KHz, 0.5W/cm 2 Ultrasonically dispersing for 1.5h, adding 8g of glutaraldehyde, heating to 48 ℃, stirring at a high speed of 1200r/min for reacting for 45min, standing for 2h, centrifuging at a high speed of 4500r/min for 10min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/cellulose gel;
4): and (3) carrying out hot-press molding on the graphene/cellulose gel obtained in the step 3) at the temperature of 60 ℃ for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 6: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1): same as step 2) of example 3;
2): same as step 3 of example 3);
3): fully dispersing 10g of hemicellulose (weight average molecular weight 27000 and dispersion coefficient 1.5) in 1990g of alkaline urine solution, adding 48mg of graphene oxide, 12mg of nitrogen-doped graphene obtained in the step 1) and 1.4mg of cerium-doped carbon quantum dots obtained in the step 2); 45KHz, 0.5W/cm 2 Ultrasonic dispersing for 1.5h, adding 8g glutaraldehyde, heating to 48 deg.C, stirring at 1200r/min for 45min, standing for 2h at 4500r/minCentrifuging for 10min, washing with distilled water and acetone in sequence, and air-drying in water bath at 60 ℃ to obtain graphene/hemicellulose gel;
4): and (3) carrying out hot-press molding on the graphene/hemicellulose gel obtained in the step 3) at the temperature of 60 ℃ for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 7: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1): same as step 1) of example 3;
2): same as step 3 of example 3);
3): fully dissolving 10g of the carboxymethyl hemicellulose obtained in the step 1) in 1990g of an alkaline urine solution, and adding 60mg of graphene oxide and 1.4mg of the cerium-doped carbon quantum dots obtained in the step 2); 45KHz, 0.5W/cm 2 Ultrasonically dispersing for 1.5h, adding 8g of glutaraldehyde, heating to 48 ℃, stirring at a high speed of 1200r/min for reaction for 45min, standing for 2h, centrifuging at a high speed of 4500r/min for 10min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
4): and (3) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step 4) at the temperature of 60 ℃ for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 8: a low-resistance high-transparency conductive film:
the embodiment provides a low-resistance high-transparency conductive film, which is prepared by the following steps:
1): same as step 1) of example 3;
2): same as step 2) of example 3;
3): adding 6g of PEG-800 into 200g of 12% dilute hydrochloric acid solution at 84 ℃, continuously stirring for 45min at 600r/min to form uniform and transparent liquid, heating at 180 ℃ for 15min to obtain black blocks, dissolving the black blocks with a large amount of deionized water, centrifuging at 3000r/min at a high speed for 10min, taking supernatant, dialyzing, and freeze-drying to obtain the carbon quantum dots;
4): taking 10g of the carboxymethyl hemicellulose obtained in the step 1) and fully dissolving the carboxymethyl hemicellulose in 1990Adding 48mg of graphene oxide, 12mg of nitrogen-doped graphene obtained in the step 2) and 1.4mg of carbon quantum dots obtained in the step 3) into the alkaline urine solution; 45KHz, 0.5W/cm 2 Ultrasonically dispersing for 1.5h, adding 8g of glutaraldehyde, heating to 48 ℃, stirring at a high speed of 1200r/min for reaction for 45min, standing for 2h, centrifuging at a high speed of 4500r/min for 10min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
5): and (3) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step 4) at the temperature of 60 ℃, for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 9: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1): same as step 1) of example 3;
2): same as step 2) of example 3);
3): fully dissolving 10g of carboxymethyl hemicellulose obtained in the step 1) in 1990g of alkaline urine solution, and adding 48mg of graphene oxide and 12mg of nitrogen-doped graphene obtained in the step 2); 45KHz, 0.5W/cm 2 Ultrasonically dispersing for 1.5h, adding 8g of glutaraldehyde, heating to 48 ℃, stirring at a high speed of 1200r/min for reaction for 45min, standing for 2h, centrifuging at a high speed of 4500r/min for 10min, washing with distilled water and acetone in sequence, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
4): and (4) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step 3) at the temperature of 60 ℃, for 2h and under the pressure of 65pa to obtain the low-resistance high-transparency conductive film.
Example 10: another low resistance, high transparency conductive film:
the embodiment provides another low-resistance high-transparency conductive film, which is prepared by the following method:
1) adding 3g of cotton into 97g of alkaline urine solution, and freezing for 1h at-15 ℃; continuously stirring for 30min for thawing, and centrifuging at 4500r/min for 10min to obtain cellulose solution; adding 10mg of graphene, and stirring for 30min at-15 ℃ to obtain a graphene/cellulose solution; adding 2g of glutaraldehyde into 100mL of graphene/cellulose solution, heating to 40 ℃, stirring for 1h at 300r/min, forming gel under the condition of water bath, and replacing in deionized water until the pH value is 7 to obtain graphene/cellulose gel;
2) and (2) carrying out hot-press molding on the graphene/cellulose gel obtained in the step 1) at the temperature of 60 ℃ for 1.5h and under the pressure of 80Pa to obtain the low-resistance high-transparency conductive film.
Experimental example 1: and (3) detecting the performance of the conductive film:
the performance of the conductive films obtained in examples 1 to 10 was measured according to the prior art, and the results are shown in table 1.
TABLE 1 results of conductive film Performance test
As can be seen from table 1, the conductive film obtained in the embodiments of the present application has excellent conductivity, light transmittance and mechanical properties, the resistivity of the conductive film is generally lower than 230 Ω · m, and the light transmittance is higher than 92%, which is superior to that of ordinary glass (about 90%), and comparative analysis shows that the light transmittance and conductivity of the conductive film can be significantly improved by performing carboxymethyl modification on hemicellulose, doping a part of nitrogen-doped graphene, adding cerium-doped carbon quantum dots, and the like.
Experimental example 2: detection of resistance of conductive film:
the conductive films obtained in examples 1 to 10 were respectively bent, and then performance tests were performed on the conductive films, and the test results are shown in tables 2 to 3.
TABLE 2 results of testing the resistance of the conductive film after bending 10 times
TABLE 3 results of conductive film resistance test after bending 100 times
As can be seen from tables 2 to 3, the conductive films obtained in the embodiments of the present application have excellent bending resistance, the transmittance of the conductive film is not lower than 90% when the conductive film is bent for 100 times, and the resistivity of the conductive film is not higher than 240 Ω · m, which indicates that the conductive film with excellent bending resistance can be obtained according to the scheme of the present application, and it should be seen that, when the cerium-doped carbon quantum dots are added to the graphene conductive film, the bending resistance of the conductive film is significantly improved, and the conductivity of the conductive film is not significantly attenuated after the conductive film is bent for multiple times, so that the conductive film can be reused, and the cost is significantly reduced.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by representative examples 1 to 10 and experimental examples 1 to 2.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
Claims (8)
1. A preparation method of a low-resistance high-transparency conductive film is characterized by comprising the following steps:
dispersing carboxymethyl hemicellulose and graphene in an alkaline urine solution, adding a cross-linking agent to prepare graphene/carboxymethyl hemicellulose gel, and performing hot-press molding to obtain a conductive film;
the carboxymethyl hemicellulose is prepared by carboxylation of hemicellulose through etherification reaction;
the weight average relative molecular mass of the hemicellulose is 20000-100000, and the dispersion coefficient is 1.2-2.0.
2. The method for producing a low-resistance high-transparent conductive film according to claim 1, characterized in that: the method specifically comprises the following steps:
s1: dispersing the dried hemicellulose into sufficient deionized water at 55-60 ℃, and adding a sodium hydroxide solution for constant-temperature alkalization reaction for at least 10 min; then adding sodium chloroacetate with the weight not less than that of the hemicellulose, heating to 65-68 ℃, adding a sodium hydroxide solution, carrying out constant-temperature etherification reaction for at least 75min, neutralizing the reaction system to be neutral by using an acetic acid solution, precipitating with absolute ethanol, washing, dialyzing for 7d, and carrying out freeze drying to obtain carboxymethyl hemicellulose;
s2: preparing an alkaline urine solution containing 0.5-1.0% of carboxymethyl hemicellulose, adding graphene which accounts for 0.4-0.8% of the weight of the carboxymethyl hemicellulose, ultrasonically dispersing for at least 1h, adding a cross-linking agent, heating to 42-50 ℃, stirring at a high speed for reaction for at least 30min, standing for 2-3 h, washing with distilled water and acetone in sequence after high-speed centrifugation, and air-drying in a water bath at 60 ℃ to obtain graphene/carboxymethyl hemicellulose gel;
s3: and (4) carrying out hot press molding on the graphene/carboxymethyl hemicellulose gel obtained in the step S2 to obtain the conductive film.
3. The method for producing a low-resistance high-transparent conductive film according to claim 1 or 2, characterized in that: the graphene contains 10-30% of nitrogen-doped graphene.
4. The method for producing a low-resistance high-transparent conductive film according to claim 3, characterized in that: the nitrogen-doped graphene is prepared by the following method: preparing a graphene dispersion liquid, adding urea according to the weight ratio of 1: 5-15 of graphene to urea, carrying out hydrothermal reaction for 6-12 h at 160-180 ℃ after complete dissolution, taking out gel, carrying out heat preservation for at least 1h at 1000-1050 ℃ under the environment of high-purity argon, and naturally cooling to obtain the graphene gel.
5. The method for producing a low-resistance high-transparent conductive film according to claim 2, characterized in that: with the addition of graphene, cerium-doped carbon quantum dots with the weight of 0.012-0.015% of that of carboxymethyl hemicellulose are also added into the alkaline urine solution of the carboxymethyl hemicellulose.
6. The method for producing a low-resistance high-transparent conductive film according to claim 5, characterized in that: the cerium-doped carbon quantum dot is prepared by the following steps: dissolving cerium oxalate in sufficient 10-15% dilute hydrochloric acid solution, continuously stirring for at least 45min at 80-85 ℃ at 300-900 r/min, then adding polyethylene glycol with the weight 5-8 times of that of the cerium oxalate, continuously stirring for at least 30min to form uniform and transparent liquid, heating for at least 10min at 120-200 ℃ to obtain black blocks, dissolving the black blocks with a large amount of deionized water, centrifuging at high speed of 1500-6000 r/min, taking supernatant, dialyzing, and freeze-drying to obtain the cerium oxalate.
7. The method for producing a low-resistance high-transparent conductive film according to any one of claims 1, 2, 4, 5 or 6, characterized in that: the hot pressing conditions are as follows: the temperature is 45-70 ℃, the time is 1.0-4.0 h, and the pressure is 50-80 pa.
8. A conductive film obtained by the method for producing a low-resistance, high-transparency conductive film according to any one of claims 1 to 7.
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