CN114436248A - Preparation method of laser-induced graphene, laser-induced graphene and application - Google Patents
Preparation method of laser-induced graphene, laser-induced graphene and application Download PDFInfo
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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Abstract
The invention discloses a preparation method of laser-induced graphene, the laser-induced graphene and application, and relates to the technical field of graphene. The preparation method of the laser-induced graphene takes chitosan hydrochloride which is highly water-soluble, biocompatible and biodegradable as a raw material, prepares the laser-induced graphene by a laser-induced method, does not need any chemical treatment in the preparation process, has simple and easy process, and is suitable for industrial application. The prepared laser-induced graphene can be further prepared into electronic devices such as a super capacitor and a sensor, and has wide application prospect in the field of manufacturing and packaging of advanced semiconductor devices.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of laser-induced graphene, the laser-induced graphene and application.
Background
Graphene (Graphene) is a carbon material with a two-dimensional layered structure, is a single-layer graphite sheet obtained by processing a bulk graphite crystal to a certain degree, and has a structure of sp2The hybridized carbon atoms form a honeycomb two-dimensional plane containing a regular hexagon, and the connection mode of the carbon atoms in the structure is the same as that of carbon materials such as zero-dimensional fullerene, one-dimensional carbon nano tube, three-dimensional graphite and the like. Since graphene has a unique two-dimensional planar structure, the graphene has very excellent properties in the aspects of electricity, thermal, optics, mechanics and the like, and has very wide prospects in various aspects of electronic information, aerospace, energy conservation, environmental protection, biomedicine, energy storage equipment, energy source, thermal management and the like, and is called as' the king of new materials”。
Graphene is strictly a single-layer structure, but in practical applications, few-layer graphene also often exhibits excellent engineering properties, and therefore, the basic consensus in the industry is: structures of 10 layers and even thicker are all collectively referred to as graphene materials. Among the materials, the three-dimensional porous graphene has a high surface area, and also maintains high electron mobility and mechanical stability, and is widely applied to various fields such as supercapacitors, sensors, catalysis, environmental remediation and gas adsorption.
The traditional three-dimensional porous graphene structure manufacturing method mainly comprises the following steps: (1) assembling Graphene Oxide (GO) into a foam, this approach requires preparation of graphene oxide precursors through its oxidation acid synthesis route. (2) Chemical Vapor Deposition (CVD) on porous substrates can also produce three-dimensional porous graphene, but high temperature conditions and subsequent etching and drying processes can prevent its scale-up. (3) A simple, scalable method has recently been developed, i.e. laser engraving of carbon rich substrates to obtain three-dimensional porous graphene, this product also being referred to as Laser Induced Graphene (LIG).
In general, the preparation process of the laser-induced graphene is as follows: under normal ambient conditions, by commercial CO2The infrared laser engraving machine irradiates a carbon-containing precursor material such as Polyimide (PI) under certain laser power, the carbon-containing precursor is converted into LIG through photochemical and thermochemical processes and the like, other parts are emitted in a gas form, and the formation of a three-dimensional porous structure of the LIG is promoted by the generation of the gas. Due to CO2An infrared laser is a common tool in a mechanical workshop, so that the method for preparing laser-induced graphene (LIG) by the one-step method has significant advantages compared with the traditional 3D graphene synthesis method. Compared with a method for reducing graphene by laser (the GO thin film is reduced into graphene by laser), the method has the advantages that the process flow is simplified by avoiding the use of GO precursors, and the cost is reduced. Particularly, the method can be used for patterning LIG obtained by a one-step method through computer program design, and greatly promotes the three-dimensional porous graphene to be electrically connected with a super capacitor, a sensor and the likeApplication in the field of sub-devices.
At present, the precursors that can be used to prepare LIG are carbon-rich materials, mainly two main types, one being polymeric plastics, represented by PI, and the other being materials rich in cellulose or lignin (such as wood, paper, bread, even potatoes). However, the former is expensive and easily pollutes the environment; the latter often requires flame retardant treatment before laser irradiation due to the low ignition point of the material. In addition, cellulose and lignin have extremely low solubility, and are not easy to prepare into films, so that the application of laser-induced graphene is limited to a certain extent.
Therefore, the search for new LIG precursors remains an important issue. In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of laser-induced graphene, and aims to provide a precursor material which is highly water-soluble, biocompatible and biodegradable, and the graphene material is prepared by laser induction without any chemical treatment.
The invention also aims to provide laser-induced graphene which is good in biodegradability and short in preparation process.
The third purpose of the present invention is to provide an application of the laser-induced graphene in the preparation of electronic devices.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing laser-induced graphene, including: performing laser-induced reduction on chitosan hydrochloride to prepare laser-induced graphene; the structural formula of the cation part in the chitosan hydrochloride is as follows:
wherein n is an integer greater than 1.
In an alternative embodiment, the chitosan hydrochloride has a molecular weight of 550-650 and a degree of deacetylation greater than 80%.
In an alternative embodiment, the chitosan hydrochloride powder is directly subjected to laser-induced reduction by using a laser.
In an alternative embodiment, the chitosan hydrochloride solution is obtained after the chitosan hydrochloride is dissolved, the chitosan hydrochloride solution is vacuumed and defoamed, then the chitosan hydrochloride solution is coated on a mold for drying and film forming, and a laser is adopted to perform laser-induced reduction on the film-shaped sample.
In an alternative embodiment, a blending raw material selected from at least one of coke, charcoal, graphite, graphene oxide, cellulose, and lignin is added during the preparation of the chitosan hydrochloride solution.
In an alternative embodiment, the process of drying to form a film comprises first drying at 60-80 ℃, and then performing second drying at 20-30 ℃ until the drying is complete;
preferably, the drying time of the primary drying is 25-40h, and the drying time of the secondary drying is 15-30 h.
In an alternative embodiment, the laser is an infrared laser;
preferably, a carbon dioxide laser in an infrared laser is adopted, and primary laser reduction and secondary laser reduction are sequentially carried out in the laser-induced reduction process, wherein the primary laser reduction is carried out by controlling the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5 and the laser power to be 5.4-5.8% of the rated power of 40W; the secondary laser reduction is to control the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5 and the laser power to be 4.8-5.2% of the rated power of 40W.
In alternative embodiments, the concentration of chitosan hydrochloride in the chitosan hydrochloride solution is 0.01-0.20 g/mL;
preferably, the vacuum defoaming is carried out in a vacuum drier for 8-15min by vacuumizing.
In a second aspect, the present invention provides a laser-induced graphene prepared by the preparation method according to any one of the preceding embodiments.
In a third aspect, the present invention provides the use of the laser-induced graphene of the foregoing embodiments in the manufacture of an electronic device, including semiconductor device fabrication and packaging.
The invention has the following beneficial effects: the chitosan hydrochloride which is highly water-soluble, biocompatible and biodegradable is used as a raw material, the laser-induced graphene is prepared by a laser-induced method, no chemical treatment is performed in the preparation process, the process is simple and easy to implement, and the method is suitable for industrial application. The prepared laser-induced graphene can be further prepared into electronic devices such as super capacitors and sensors, and has wide application prospects.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a technical scheme for realizing preparation of various graphene materials by laser-induced chitosan hydrochloride;
FIG. 2 is a flow chart of an embodiment;
FIG. 3 is a text flow diagram of an embodiment;
FIG. 4 is a Raman spectrum of a chitosan hydrochloride laser-induced graphene material;
fig. 5 is a scanning electron microscope image of chitosan hydrochloride laser-induced graphene.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The inventor makes continuous attempts to the laser-induced precursor material through long-term continuous exploration, and finally discovers that: the chitosan hydrochloride is adopted as the precursor, so that the defects in the prior art can be overcome, and the method has the following advantages: (1) the water-soluble film can be highly water-soluble, is easy to form a film and lays a foundation for wide application; (2) the graphene material is biocompatible and biodegradable, and is an environment-friendly product; (3) the preparation process does not need chemical treatment such as flame retardance, and the process is simple, convenient and feasible and is suitable for industrial application.
Chitosan is a linear, semi-crystalline cationic polysaccharide produced by deacetylation of the chitin moiety, the second most abundant natural biopolymer in nature. It has the characteristics of wide sources, low-cost extraction, biocompatibility, biodegradability and the like. However, the use of chitosan is limited by its inherent inability to dissolve directly in water. Due to the abundant substitution and crosslinking sites on the structure and the cleavable property of the high molecular polymer chain, a large number of functional water-soluble chitosan derivatives, such as chitosan hydrochloride, are developed.
Chitosan hydrochloride is a strong cationic water-soluble chitosan derivative, and is generally obtained by protonating and modifying chitosan. Compared with chitosan, the chitosan hydrochloride has obviously increased water solubility, but other physiological characteristics and functional properties are basically reserved, so that the application of the chitosan compound is greatly expanded.
The embodiment of the invention provides a preparation method of laser-induced graphene, which comprises the following steps: performing laser-induced reduction on chitosan hydrochloride to prepare laser-induced graphene; the structural formula of the cation part in the chitosan hydrochloride is as follows:
wherein n is an integer greater than 1.
In some embodiments, the chitosan hydrochloride has a molecular weight of 550-650 and a degree of deacetylation greater than 80%. The molecular weight of the chitosan hydrochloride is controlled within the range, the chitosan hydrochloride is too large and too viscous to remove air bubbles easily, and the uniformity of the obtained material is poor.
Referring to fig. 1, the method for preparing graphene by using chitosan hydrochloride is roughly divided into three implementation forms, which specifically include: (1) the method comprises the following steps of directly carrying out laser-induced reduction on chitosan hydrochloride powder by adopting a laser, so as to prepare graphene, graphene quantum dots or graphene mesoporous materials; (2) dissolving chitosan hydrochloride to obtain a chitosan hydrochloride solution, performing vacuum defoaming on the chitosan hydrochloride solution, coating the chitosan hydrochloride solution on a mold for drying and film forming, and performing laser-induced reduction on a film-shaped sample by using a laser, wherein the film-shaped sample can be used for preparing graphene or a graphene mesoporous material as shown in fig. 2 and 3; (3) the chitosan hydrochloride solution is mixed and dissolved with the blending raw material and the solvent to obtain the chitosan hydrochloride solution, the chitosan hydrochloride solution is subjected to vacuum defoaming, then the chitosan hydrochloride solution is coated on a mold to be dried and formed into a film, and a laser is adopted to carry out laser-induced reduction on the film-shaped sample, so that the chitosan hydrochloride solution can be used for preparing graphene or graphene composite materials.
Specifically, the blending raw material is selected from at least one of coke, charcoal, graphite, graphene oxide, cellulose and lignin, and the blending raw material may be one or more of the above materials, which is not limited herein. The doped raw materials are added to endow the graphene material with more functions so as to meet different application requirements.
In some embodiments, the concentration of chitosan hydrochloride in the chitosan hydrochloride solution is 0.01-0.20g/mL, specifically can be 0.01g/mL, 0.02g/mL, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL, 0.10g/mL, 0.11g/mL, 0.12g/mL, 0.13g/mL, 0.14g/mL, 0.15g/mL, 0.16g/mL, 0.17g/mL, 0.18g/mL, 0.19g/mL, 0.20g/mL, and the like, and can also be any value between the adjacent concentration values above.
Specifically, the solvent used for preparing the chitosan hydrochloride solution can be water, and can also be prepared by other organic solvents, which are not listed here.
In some embodiments, the vacuum debubbling is carried out in a vacuum drier for 8-15min by vacuum pumping. The chitosan hydrochloride with larger molecular weight can rapidly achieve the aim of defoaming by adopting a vacuum defoaming mode, and the time of vacuumizing treatment can be 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min and the like, and can also be any value between the adjacent time values.
Specifically, the mold (or film forming tool) for film formation may be a general box mold, and the bottom surface may be a flat surface, and the chitosan hydrochloride solution may be applied to the mold, and a thin film sample may be obtained after drying.
In some embodiments, the process of drying to form a film comprises first drying at 60-80 ℃ and then drying at 20-30 ℃ for the second time until the drying is complete; the drying time of the primary drying is 25-40h, and the drying time of the secondary drying is 15-30 h. The inventor finds that the chitosan hydrochloride can be curled and cannot form a flat film if the chitosan hydrochloride is completely dried under the condition of 60-80 ℃; by adopting a two-step drying mode, the phenomenon of curling can be avoided, and the chitosan hydrochloride film-shaped sample with smaller tortuosity and film stress is obtained. Specifically, the drying and film forming method is not limited, and a method of baking the film in an oven at a high temperature may be employed, or the film may be dried by a vacuum dryer.
Specifically, the temperature of the primary drying may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like, or may be any value between the above adjacent temperature values; the time for primary drying may be 25h, 28h, 30h, 32h, 35h, 38h, 40h, etc., or may be any value between the above adjacent time values. The temperature of the secondary drying can be 25 ℃, 28 ℃, 30 ℃, 33 ℃, 35 ℃, 38 ℃, 40 ℃ and the like, and can also be any value between the adjacent temperature values; the time for the secondary drying may be 15h, 18h, 20h, 22h, 25h, 28h, 30h, etc., or may be any value between the above adjacent time values.
Further, a laser is adopted to carry out laser-induced reduction on the film-shaped sample, and chitosan hydrochloride is quickly carbonized to form the porous graphene by utilizing the high temperature of the laser irradiating the surface of the film-shaped sample. The laser is an infrared laser, and the chitosan hydrochloride can be quickly carbonized.
In some embodiments, a carbon dioxide laser in an infrared laser is used, and a primary laser reduction and a secondary laser reduction are sequentially performed in the laser-induced reduction process, wherein the primary laser reduction is performed by controlling the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5, and the laser power to be 5.4-5.8% of the rated power of 40W (such as 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, and the like); the secondary laser reduction is to control the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5 and the laser power to be 4.8-5.2% (such as 4.8%, 4.9%, 5.0%, 5.1%, 5.2% and the like) of the rated power of 40W.
The inventors found that the quality of the obtained graphene material is relatively poor if only one laser reduction is performed, the 2D characteristic peak obtained from raman characterization has low intensity and wide peak, and the number of graphene layers is large.
Specifically, the step speed of the two laser reductions can be 25mm/s, 26mm/s, 27mm/s, 28mm/s, 29mm/s, 30mm/s, 31mm/s, 32mm/s, 33mm/s, 34mm/s, 35mm/s, and the like, and can also be any value between the above adjacent step speeds; the step pixels may be 1, 2, 3, etc.
The embodiment of the invention also provides laser-induced graphene, which is prepared by the preparation method in the embodiment, the preparation process is simple and easy to implement, chemical treatment is not required, the product can be in various forms, and can be graphene quantum dots, graphene mesoporous materials, graphene composite materials and the like, and electronic devices such as super capacitors and sensors which are environment-friendly and human-friendly can be further prepared and formed.
In addition, due to the excellent electric and heat conducting performance of the laser-induced graphene, the graphene can have potential utilization value in the fields of advanced semiconductor device manufacturing and packaging, such as chip three-dimensional integration, advanced packaging material preparation, 5G radio frequency chip packaging and the like.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of laser-induced graphene, which comprises the following steps:
(1) 10g of chitosan hydrochloride powder (molecular weight is 610.866) is weighed and poured into a beaker, then 150mL of deionized water is added, and the chitosan hydrochloride solution is obtained by slowly dissolving under the stirring of a magnetic stirrer.
(2) And transferring the beaker filled with the chitosan hydrochloride solution into a vacuum drier, and carrying out vacuum pumping treatment for 10min under low vacuum to obtain the uniform bubble-free chitosan hydrochloride solution.
(3) 20mL of chitosan hydrochloride solution was pipetted into a plastic round sample box with a diameter of 66mm and a height of 12 mm.
(4) And transferring the round plastic box and the contained chitosan hydrochloride liquid into a vacuum drier, drying at 70 ℃ for 36 hours, transferring the incompletely dried sample to room temperature (25 ℃) for further slow drying for 24 hours, and drying in two steps to obtain the chitosan hydrochloride film-shaped sample with small tortuosity and film stress.
(5) With commercial CO2And (3) carrying out induced reduction on the chitosan hydrochloride film-shaped sample by using a laser in an environmental atmosphere, and quickly carbonizing the chitosan hydrochloride to form the porous graphene by using the high temperature of the surface of the film-shaped sample irradiated by using the laser. Two steps of laser irradiation are used, the first laser condition is that a laser spot is focused on the surface of a sample, the stepping speed is 30mm/s, the stepping pixel is 2, and the laser power is 5.6 percent of the rated power (40W) of the laser. The second laser condition is that the laser spot is focused on the surface of the sample, the stepping speed is 30mm/s, the stepping pixel is 2, and the laser power is 5.0 percent of the rated power (40W) of the laser.
Example 2
The embodiment provides a preparation method of laser-induced graphene, which comprises the following steps: to prepare the chitosan hydrochloride solution, 3g of cellulose was added.
The inventors have found that the addition of cellulose may have the following advantages: (1) the chitosan hydrochloride can be used for flame retardance of cellulose, so that the chitosan hydrochloride can be converted into LIG without flame retardance under the atmosphere of normal temperature and normal pressure, and the obtained product has better quality, which is specifically represented by the following steps: the number of graphene layers is less, and the conductivity is stronger.
Comparative example 1
The present comparative example provides a method for preparing laser-induced graphene, which is different from example 1 only in that: the chitosan hydrochloride is replaced by chitosan with the same amount (the deacetylation degree is more than or equal to 95 percent), the chitosan hydrochloride is dissolved by acetic acid solution with the same volume fraction of 5 percent, and the chitosan membrane obtained after the same operation is treated by a laser under the same condition.
The results show that: the target product LIG cannot be obtained under various laser conditions.
Test example 1
The raman spectrum of the product obtained in example 1 was measured, and the result is shown in fig. 4.
As can be seen from fig. 4, characteristic peaks such as G peak, D peak and 2D peak in the raman spectrum indicate that the obtained product is LIG, i.e. laser-induced graphene, wherein a higher D peak indicates that the obtained LIG has more defect states, which is consistent with the reported LIG characteristics. In addition, the sharp 2D peak indicates the low layer character of the resulting LIG. The raman spectra qualitatively characterize the resulting LIG.
Test example 2
An electron micrograph of the graphene material obtained in test example 1 is shown in fig. 5, in which (a) to (b) are 100 μm and 10 μm, respectively, in fig. 5.
As can be seen from fig. 5, the prepared graphene exhibits a sheet-like characteristic and has a porous structure, and the size of the pores varies from several micrometers to tens of micrometers, which is consistent with the characteristics of the three-dimensional porous graphene reported in the literature.
In summary, the invention provides a preparation method of laser-induced graphene, the laser-induced graphene and an application thereof, and the laser-induced graphene is prepared by using chitosan hydrochloride which is highly water-soluble, biocompatible and biodegradable as a raw material and by using a laser-induced method. The raw material chitosan hydrochloride powder required by the method is green and environment-friendly, can be used for preparing a film or mixing other substances for pulping, has simple and efficient preparation process and low production cost, and is suitable for mass production of functionalized graphene materials.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of laser-induced graphene is characterized by comprising the following steps: performing laser-induced reduction on chitosan hydrochloride to prepare the laser-induced graphene; the structural formula of the cation part in the chitosan hydrochloride is as follows:
wherein n is an integer greater than 1.
2. The method as claimed in claim 1, wherein the molecular weight of the chitosan hydrochloride is 550-650 and the degree of deacetylation is greater than 80%.
3. The preparation method according to claim 2, wherein the chitosan hydrochloride powder is directly subjected to laser-induced reduction by using a laser.
4. The preparation method according to claim 2, characterized in that the chitosan hydrochloride solution is obtained after dissolving the chitosan hydrochloride, the chitosan hydrochloride solution is vacuumed, and then coated on a mold for drying and film forming, and the film-shaped sample is subjected to laser-induced reduction by a laser.
5. The method according to claim 4, wherein a blending raw material selected from at least one of coke, charcoal, graphite, graphene oxide, cellulose, and lignin is added during the preparation of the chitosan hydrochloride solution.
6. The preparation method according to claim 4, wherein the drying to form the film comprises performing primary drying at 60-80 ℃, and then performing secondary drying at 20-30 ℃ until the drying is complete;
preferably, the drying time of the primary drying is 25-40h, and the drying time of the secondary drying is 15-30 h.
7. The method of manufacturing according to claim 4, wherein the laser is an infrared laser;
preferably, the laser adopts a carbon dioxide laser in an infrared laser, and primary laser reduction and secondary laser reduction are sequentially carried out in the laser-induced reduction process, wherein the primary laser reduction is carried out by controlling the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5 and the laser power to be 5.4-5.8% of the rated power of 40W; the secondary laser reduction is to control the stepping speed to be 25-35mm/s, the stepping pixel to be 1-5 and the laser power to be 4.8-5.2% of the rated power of 40W.
8. The production method according to claim 4, wherein the concentration of the chitosan hydrochloride in the chitosan hydrochloride solution is 0.01 to 0.20 g/mL;
preferably, the vacuum defoaming is carried out in a vacuum drier for 8-15min by vacuumizing.
9. Laser-induced graphene prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the laser-induced graphene according to claim 9 for the preparation of an electronic device;
preferably, preparing the electronic device includes semiconductor device fabrication and packaging.
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