CN112265983A - Lignin graphene and preparation method thereof - Google Patents
Lignin graphene and preparation method thereof Download PDFInfo
- Publication number
- CN112265983A CN112265983A CN202011177566.3A CN202011177566A CN112265983A CN 112265983 A CN112265983 A CN 112265983A CN 202011177566 A CN202011177566 A CN 202011177566A CN 112265983 A CN112265983 A CN 112265983A
- Authority
- CN
- China
- Prior art keywords
- lignin
- graphene
- laser
- ball milling
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004590 computer program Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 14
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000284 resting effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002113 nanodiamond Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 sensors Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The preparation method of the lignin graphene comprises the steps of performing ball milling on lignin by a ball mill, and pressing dry lignin powder into small sheets by a mould; and (3) placing the lignin slice on an XY workbench controlled by a computer program, and performing laser radiation at normal temperature and normal pressure by using a femtosecond laser to finally obtain graphene powder. The method has the advantages of cheap and easily-obtained raw materials, mild synthesis conditions, high efficiency, simple operation and good conductivity of the obtained graphene.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to lignin graphene and a preparation method thereof.
Background
Carbon materials have been extensively studied in the past few decades for their high thermal stability and mechanical properties. Graphene is a sp2 hybridized carbon nanoparticle, and is an allotrope with carbon nanotubes, fullerenes, nanodiamonds, and the like. The graphene has excellent conductivity, heat conductivity, mechanical property and magnetic property, and has wide application prospect in the fields of energy storage materials, sensors, composite materials, biological medicines and the like. At present, the preparation methods of graphene mainly comprise graphene oxide reduction, Chemical Vapor Deposition (CVD), mechanical stripping, epitaxial growth and the like. However, these methods have high cost, low controllability, and low product quality, and some methods also cause environmental pollution due to the use of hazardous chemicals. Therefore, the development of a graphene preparation method which is simple to operate, safe, effective, green and environment-friendly is of great significance.
Lignin is one of the three major components of the cell wall of natural lignocellulosic plants, and is present in an amount of about 30% of the total organic carbon on earth, and is a renewable feedstock consisting exclusively of aromatic moieties. In addition to abundant natural resources, lignin is a major by-product of the pulp and paper industry. In the pulp and paper industry, about 7000 million tons of lignin are produced per year, of which only about 2% recover heat energy, replacing fossil materials by combustion. The effective utilization of lignin becomes an important part of the research on the utilization of sustainable resources. Converting lignin into graphene in this patent, the high-efficient high-quality utilization of living beings has important influence, and the graphene who obtains has potential application in aspects such as miniature ultracapacitor system, sensor, waste water treatment, functional material.
Disclosure of Invention
The technical problem to be solved is as follows: the invention overcomes the defects of high preparation cost, low controllability, low product quality and environment disadvantage of graphene in the prior art, and provides lignin graphene and a preparation method thereof. The method has the advantages of cheap and easily-obtained raw materials, mild synthesis conditions, high efficiency, simple operation and good conductivity of the obtained graphene.
The technical scheme is as follows: the method for preparing graphene from lignin comprises the following steps: (1) putting lignin into a ball mill for ball milling to 50-500nm, and drying for 1-2 h at 105 ℃ in a drying box after the ball milling is finished; (2) putting the lignin powder dried in the step (1) into a die for pressing, wherein the pressure is 5-10 MPa; (3) placing the lignin slices in the step (2) on a workbench controlled by a computer program, and performing laser radiation at normal temperature and normal pressure by using a femtosecond laser to convert the irradiated raw materials into graphene; wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, and the pulse time is 150 fs.
The lignin in the step (1) is at least one of coniferous lignin, broadleaf lignin, alkaline lignin and sodium lignosulfonate.
The laser power used in the step (3) is 100-1000 mW.
The operating speed of the workbench used in the step (3) is 1 mm/s-100 mm/s.
The laser radiation time used in the step (3) is 1-60 min.
The lignin graphene prepared by the method is provided.
Has the advantages that: according to the invention, lignin is used as a raw material, and is subjected to nanocrystallization by a high-pressure homogenizer, and the graphene is obtained by laser radiation of the dried nano lignin. The obtained nano diamond has the granularity within 100nm, and has high application value in the fields of micro supercapacitors, sensors, wastewater treatment and the like.
Drawings
Fig. 1 is a raman spectrum of graphene in example 1. Wherein 1580cm-1The peak G is a characteristic peak of sp2 bond in carbon in graphene, 1370cm-1The D peak is a carbon sp3 hybridization peak and is generated due to graphene molecular defects. And comparing the two characteristic peaks, wherein the G peak is obviously higher than the D peak, which shows that the graphene has better quality.
Fig. 2 is a transmission electron micrograph of graphene in example 1. The figure shows obvious graphene lattice fringes, and the calculated interplanar spacing is 0.34 nm.
Detailed Description
The principle of the invention is that lignin is converted into graphene through femtosecond laser radiation after ball milling, and the graphene has better conductivity. The invention is further illustrated by the following specific examples. It should be noted that the following embodiments are illustrative, and are not intended to limit the scope of the present invention. After reading the present disclosure, various changes or modifications may be made by those skilled in the art, and these equivalents also fall within the scope of the present disclosure.
Normal temperature and normal pressure: 25 ℃ and 101 KPa.
Example 1
Putting the pine lignin into a ball mill for ball milling for 18h, setting the rotating speed to be 360r/min, resting for 0.5h every 1h, and drying for 1-2 h at 105 ℃ in a drying oven after the ball milling is finished. Placing 0.2g of dry lignin powder in a mold, pressing the lignin powder into a sheet under the pressure of 10MPa, placing the lignin sheet on a workbench controlled by a computer program XY, and carrying out laser radiation by using a femtosecond laser at normal temperature and normal pressure, wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, the pulse time is 150fs, the radiation condition is that the laser power is 800mW, the radiation time is 10min, the operating speed of the workbench is 5mm/s, obtaining graphene after radiation, and testing the square resistance of the graphene to be 5 omega/□ by a four-probe tester.
The microstructure of the graphene is analyzed by Raman spectroscopy and a transmission electron microscope, and the method is shown to effectively prepare the high-quality graphene.
The raman spectrum and the transmission electron micrograph of the graphene obtained in the following examples are substantially the same as those of example 1, and therefore, they are not described in the following examples.
Example 2
Putting the pine lignin into a ball mill for ball milling for 18h, setting the rotating speed to be 360r/min, resting for 0.5h every 1h, and drying for 1-2 h at 105 ℃ in a drying oven after the ball milling is finished. Placing 0.2g of dry lignin powder in a mold, pressing the lignin powder into a sheet under the pressure of 10MPa, placing the lignin sheet on a workbench controlled by a computer program XY, and carrying out laser radiation by using a femtosecond laser at normal temperature and normal pressure, wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, the pulse time is 150fs, the radiation condition is that the laser power is 400mW, the radiation time is 40min, the operating speed of the workbench is 80mm/s, obtaining graphene after radiation, and testing the square resistance of the graphene to be 579 omega/□ by a four-probe tester.
Example 3
Putting the eucalyptus lignin into a ball mill for ball milling for 12 hours, setting the rotating speed to be 360r/min, resting for 0.5 hour every 1 hour, and drying for 1-2 hours at 105 ℃ in a drying oven after the ball milling is finished. Placing 0.2g of dry lignin powder in a mold, pressing the lignin powder into a sheet under the pressure of 10MPa, placing the lignin sheet on a workbench controlled by a computer program XY, and carrying out laser radiation by using a femtosecond laser at normal temperature and normal pressure, wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, the pulse time is 150fs, the radiation condition is that the laser power is 100mW, the radiation time is 30min, the operating speed of the workbench is 30mm/s, obtaining graphene after radiation, and testing the square resistance of the graphene to be 106 omega/□ by a four-probe tester.
Example 4
Putting the eucalyptus lignin into a ball mill for ball milling for 10 hours, setting the rotating speed to be 360r/min, resting for 0.5 hour every 1 hour, and drying for 1-2 hours at 105 ℃ in a drying oven after the ball milling is finished. Placing 0.2g of dry lignin powder in a mold, pressing the lignin powder into a sheet under the pressure of 10MPa, placing the lignin sheet on a workbench controlled by a computer program XY, and carrying out laser radiation by using a femtosecond laser at normal temperature and normal pressure, wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, the pulse time is 150fs, the radiation condition is that the laser power is 300mW, the radiation time is 20min, the operating speed of the workbench is 10mm/s, obtaining graphene after radiation, and testing the square resistance of the graphene to be 37 omega/□ by a four-probe tester.
Example 5
Putting sodium lignosulfonate into a ball mill for ball milling for 6 hours, setting the rotating speed to be 360r/min, resting for 0.5 hour every 1 hour of work, and drying for 1-2 hours at 105 ℃ in a drying oven after the ball milling is finished. Placing 0.2g of dry lignin powder in a mold, pressing the lignin powder into a sheet under the pressure of 10MPa, placing the lignin sheet on a workbench controlled by a computer program XY, and carrying out laser radiation by using a femtosecond laser at normal temperature and normal pressure, wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, the pulse time is 150fs, the radiation condition is that the laser power is 750mW, the radiation time is 60min, the operating speed of the workbench is 3mm/s, obtaining graphene after radiation, and testing the square resistance of the graphene to be 863 omega/□ by a four-probe tester.
Claims (6)
1. The method for preparing graphene from lignin is characterized by comprising the following steps:
(1) putting lignin into a ball mill for ball milling to 50-500nm, and drying for 1-2 h at 105 ℃ in a drying box after the ball milling is finished;
(2) putting the lignin powder dried in the step (1) into a die for pressing, wherein the pressure is 5-10 MPa;
(3) placing the lignin slices in the step (2) on a workbench controlled by a computer program, and performing laser radiation at normal temperature and normal pressure by using a femtosecond laser to convert the irradiated raw materials into graphene; wherein the laser wavelength of the femtosecond laser is 1030nm, the laser frequency is 120kHz, and the pulse time is 150 fs.
2. The method for preparing graphene from lignin according to claim 1, wherein the lignin in step (1) is at least one of coniferous lignin, broadleaf lignin, alkali lignin and sodium lignosulfonate.
3. The method for preparing graphene from lignin according to claim 1, wherein the laser power used in the step (3) is 100 mW-1000 mW.
4. The method for preparing graphene from lignin according to claim 1, wherein the operating speed of the workbench used in the step (3) is 1 mm/s-100 mm/s.
5. The method for preparing graphene from lignin according to claim 1, wherein the laser irradiation time used in the step (3) is 1-60 min.
6. The lignin graphene prepared by the method of any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011177566.3A CN112265983B (en) | 2020-10-29 | 2020-10-29 | Lignin graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011177566.3A CN112265983B (en) | 2020-10-29 | 2020-10-29 | Lignin graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112265983A true CN112265983A (en) | 2021-01-26 |
| CN112265983B CN112265983B (en) | 2023-11-07 |
Family
ID=74344867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011177566.3A Active CN112265983B (en) | 2020-10-29 | 2020-10-29 | Lignin graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112265983B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115092913A (en) * | 2021-09-29 | 2022-09-23 | 云南华谱量子材料有限公司 | Technology and device for preparing graphene quantum material by ultrashort pulse laser-induced pyrolysis |
| CN116947032A (en) * | 2023-07-25 | 2023-10-27 | 青岛农业大学 | Method for improving graphitization capability of lignin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170113936A1 (en) * | 2013-06-05 | 2017-04-27 | The United States Of America As Represented By The Secretary Of Agriculture | Methods for Synthesizing Graphene from a Lignin Source |
| CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
| WO2020021361A1 (en) * | 2018-07-23 | 2020-01-30 | King Abdullah University Of Science And Technology | Lignin based laser lithography process for fabricating 3d graphene electrode and method |
| CN111344253A (en) * | 2017-08-24 | 2020-06-26 | Rd石墨烯有限公司 | 3D graphene |
-
2020
- 2020-10-29 CN CN202011177566.3A patent/CN112265983B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170113936A1 (en) * | 2013-06-05 | 2017-04-27 | The United States Of America As Represented By The Secretary Of Agriculture | Methods for Synthesizing Graphene from a Lignin Source |
| CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
| CN111344253A (en) * | 2017-08-24 | 2020-06-26 | Rd石墨烯有限公司 | 3D graphene |
| WO2020021361A1 (en) * | 2018-07-23 | 2020-01-30 | King Abdullah University Of Science And Technology | Lignin based laser lithography process for fabricating 3d graphene electrode and method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115092913A (en) * | 2021-09-29 | 2022-09-23 | 云南华谱量子材料有限公司 | Technology and device for preparing graphene quantum material by ultrashort pulse laser-induced pyrolysis |
| CN115092913B (en) * | 2021-09-29 | 2023-09-19 | 云南华谱量子材料有限公司 | Technology and device for preparing graphene quantum material by ultrashort pulse laser induced cracking |
| CN116947032A (en) * | 2023-07-25 | 2023-10-27 | 青岛农业大学 | Method for improving graphitization capability of lignin |
| CN116947032B (en) * | 2023-07-25 | 2024-01-26 | 青岛农业大学 | Method for improving graphitization capability of lignin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112265983B (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Synthesis, formation mechanisms and applications of biomass-derived carbonaceous materials: a critical review | |
| Safian et al. | A review on bio-based graphene derived from biomass wastes | |
| Sun et al. | Enhanced mechanical energy conversion with selectively decayed wood | |
| Wang et al. | A new route for preparation of hydrochars from rice husk | |
| Li et al. | Cellulose whiskers extracted from mulberry: A novel biomass production | |
| CN112265983A (en) | Lignin graphene and preparation method thereof | |
| CN105713100A (en) | Method for rapidly preparing cellulose nanocrystalline | |
| Bravo et al. | Characterization of tensile damage for a short birch fiber-reinforced polyethylene composite with acoustic emission | |
| CN107128905B (en) | Method for preparing graphene from biomass derivative based on mechanochemical method | |
| CN113247884A (en) | Method for preparing graphene material by laser-induced industrial hemp | |
| CN103755817B (en) | A kind of preparation method of nano micro crystal cellulose | |
| Long et al. | Graphene two-dimensional crystal prepared from cellulose two-dimensional crystal hydrolysed from sustainable biomass sugarcane bagasse | |
| Tatrari et al. | Mass production of metal-doped graphene from the agriculture waste of Quercus ilex leaves for supercapacitors: inclusive DFT study | |
| CN104353842A (en) | Preparation method of nanosilver-graphene composite material | |
| Supriya et al. | Carbon nanospheres obtained from carbonization of bio-resource: a catalyst free synthesis | |
| CN114477151A (en) | Preparation method of graphene material, graphene material and application of graphene material | |
| Lou et al. | Fabrication of hierarchical lignin-based carbon through direct high-temperature pyrolysis and its electrochemical application | |
| CN108069415B (en) | Preparation method of pore-graded graphene aerogel | |
| CN108975322A (en) | The method for preparing graphene slurry | |
| JP4996583B2 (en) | Cellulose carbide structure having graphite nanostructure layer on the surface and synthesis method thereof | |
| CN103232031B (en) | Method for treating waste polyolefin plastics | |
| CN102120568A (en) | Method for preparing boron nitride nanorod by using precursor conversion method | |
| CN109956917A (en) | A kind of method and product of biomass coproducing furfural and carbon quantum dot | |
| CN112357918B (en) | Nano diamond prepared from plant fiber and method thereof | |
| CN112265989B (en) | Nano diamond prepared by taking plant fiber film as raw material and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |