CN115709990A - Method for preparing non-metal doped porous graphene material by laser-induced solid phase - Google Patents
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
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- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000002184 metal Chemical class 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing a non-metal doped porous graphene material by laser-induced solid phase, which comprises the steps of uniformly mixing graphene oxide powder and a non-metal element inorganic salt compound to obtain a mixed sample; and transferring the mixed sample into an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing argon/hydrogen mixed gas into the ampoule bottle, placing the ampoule bottle under a laser, and scanning the mixed sample in the ampoule bottle by using laser. And soaking the sample subjected to the laser treatment by using an acid solution, washing by using deionized water, and freeze-drying to obtain the non-metal doped porous graphene material. The process method provided by the invention realizes uniform surface treatment and modification of the powder material by laser, and has the advantages of simple and feasible scheme, good repeatability, short preparation period, simple and convenient process and easy large-scale production. Meanwhile, the nitrogen-doped graphene material prepared by the invention has high catalytic and energy storage performances, good stability and good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic nano materials for energy storage battery devices, and particularly relates to a method for preparing a non-metal doped porous graphene material by laser-induced solid phase.
Background
With the advent of the fossil energy crisis and the increasing problem of environmental pollution, the development and utilization of clean energy is imminent. The electric energy as clean energy is no exception, and the carbon-based composite material is a key electrode material for realizing the large-scale application of the miniature and flexible super capacitor. However, graphene has the defect of low electrochemical activity when used as an energy storage electrode material. Therefore, it is a new research direction to improve the electrochemical activity of graphene. By introducing non-metal heteroatoms and changing the spatial structure of the graphene, the conductivity, catalytic activity and energy storage activity of the graphene can be greatly improved. As N adjacent to C, the N is easier to act with C atoms of graphene to replace the original positions of the C atoms, so that the microstructure of the graphene is changed, and the electrochemical activity, the catalytic activity and the energy storage activity of the graphene are improved.
The research of the nonmetal-doped graphene has very high scientific and application significance, and the existing method for preparing the nitrogen-doped graphene material mainly comprises a high-temperature reduction method, a solvothermal method, a microwave method, a chemical vapor deposition method, a laser method and the like. For example, patent document CN110931736A discloses a hydrothermal method for preparing a nitrogen-doped graphene electrode material, wherein the hydrothermal reaction temperature is 160-200 ℃, the reaction time is 12-24h, the annealing temperature is 600-800 ℃, the annealing time is 600-800 ℃, and the method has high energy consumption and long preparation period. Patent document CN113479872A discloses that a one-step hydrothermal method is adopted for preparing a nitrogen-doped graphene electrode material, hydrogen peroxide is required to pretreat graphene in the preparation process, the doping purpose is achieved at a higher temperature, the operation is relatively complicated, and the finally obtained product is hydrogel. Patent document CN114360926A discloses a method for preparing a nitrogen-doped layered graphene electrode by a microwave method, wherein the microwave power is 600-1000W, and after samples are mixed in the preparation process, the samples need to be dried for 48h, which takes a long time.
The laser method is applied to the preparation of the graphene-based composite material. For example, patent No. CN104058389B discloses a method for preparing boron-doped graphene by a laser method, which utilizes a laser doping device to have a simple process, but the reaction is performed in a liquid phase during the preparation process, and concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 65% are required, so that the risk coefficient is large, the damage to the environment is also serious, and the sample in the solution wastes laser power. For preparing the nitrogen-doped graphene by the chemical vapor deposition method, the experimental process has high requirements on equipment, is not suitable for large-scale preparation and has high energy consumption.
The composite material of graphene and metal salt can also be prepared by a laser method. For example, patent document No. CN110586156A discloses a preparation method of mesoporous nitrogen doped graphene loaded molybdenum disulfide by laser irradiation synthesis, which comprises the steps of dispersing graphene oxide in absolute ethyl alcohol, treating for 20-30min with laser pulses, performing freeze drying, doping with N, N-dimethylformamide as a nitrogen source, mixing with tetrathiomolybdic acid, reacting for 12-16h by a hydrothermal method, and performing freeze drying again to obtain a product. The preparation process needs to carry out laser treatment on the sample in the solution, the energy loss is serious, and freeze drying is carried out twice, so that the operation is complicated. Patent publication No. CN11422914A discloses a laser-induced graphene loaded iron dopingThe preparation method of the cobalt disulfide comprises the steps of pretreating experimental raw materials, namely carrying out laser treatment on graphene and Fe-CoS 2 And then a hydrothermal reduction method is adopted to obtain a product. The processing of the sample with more steps is more complicated, and the requirement on the sample is higher. Patent document No. CN109289892B discloses a method for preparing a manganese-based mullite/nitrogen-doped graphene composite oxygen-containing catalyst, which comprises the steps of carrying out laser pretreatment on a mullite suspension, mixing the mullite suspension with graphene oxide and ammonium bicarbonate after drying, drying the liquid after hydrothermal reaction for 10-15h again, dispersing the dried sample in deionized water for secondary laser treatment, washing and drying to obtain the product. The preparation process needs two times of laser treatment on the sample suspension, and the hydrothermal method is long in time consumption and is not suitable for large-scale production.
In addition, the laser method is also used for preparing the graphene and metal oxide composite material. For example, patent document No. CN109590008B discloses a method for preparing vacancy-adjustable cobaltosic oxide nitrogen-doped graphene by laser synthesis, which comprises the steps of dispersing graphene oxide in an organic solvent, adding other raw materials, performing oil bath at 80 ℃ for 10 hours, performing hydrothermal reaction for 3 hours, performing freeze drying, dissolving the freeze-dried sample in deionized water for laser treatment, and performing freeze drying on the sample again to obtain the product. Two times of freeze drying are needed in the preparation process, the energy consumption is high when the sample in the solution is subjected to laser treatment, and the experimental period is long. In order to realize the uniform action of laser and substances, most of the existing processes are compounded or doped in a solution, so that the solution-based scheme is not only unfavorable for the absorption of laser energy by graphene, but also causes environmental burden due to volatilization of an organic solvent in the process.
The patent document with publication number CN114093681A discloses laser sulfur-doped graphene/MnO-Mn 3 O 4 The method for preparing the composite electrode material comprises the steps of preparing a graphene oxide/manganese sulfate coating from raw materials, coating the graphene oxide/manganese sulfate coating on a PI substrate, drying the coating at room temperature, and carrying out laser treatment to obtain a sulfur-doped graphene/MnO-Mn product 3 O 4 A composite electrode material. The sample is required to be pretreated, the operation is complicated, and the experiment period is long. Publication No. asCN114093682A discloses a laser preparation method of a graphene/Co-CoO composite electrode material, which comprises preparing a coating from graphene oxide and cobalt acetate, coating the coating on a PI substrate, drying at room temperature, and performing laser treatment to obtain the product. Patent document CN109682872A discloses a method for preparing a laser-induced titanium dioxide/three-dimensional porous graphene composite photoelectrode, which comprises mixing 4, 4-diaminodiphenyl ether, N-dimethylformamide, pyromellitic dianhydride and a titanium source to prepare a coating, coating the coating on indium tin oxide conductive glass, dehydrating to prepare a titanium ion-doped polyimide film, and performing laser treatment to directly generate the titanium dioxide/three-dimensional porous graphene composite photoelectrode on the surface of the indium tin oxide conductive glass.
Patent document CN104609404A discloses a method for preparing graphene and composite materials by sunlight and laser reduction, which uses sunlight and laser to process a graphene bulk material, and the laser heating method has inhomogeneity, so that the uniform heating of the sunlight and the laser to the inside and the outside of the bulk material cannot be realized in the process of heating the bulk material. In this patent document, it is mentioned that the surface modification or doping treatment is performed on the graphene oxide bulk material by using laser, but since the interior of the graphene oxide bulk material cannot directly receive irradiation energy of sunlight or laser, a uniformly doped graphene material cannot be obtained. The scheme mainly aims at the treatment of materials with certain macroscopic shapes, and uniform preparation or treatment of solid powder materials by laser cannot be realized.
In addition, patent with application publication number CN102191485A, a method for growing graphene by laser is indicated; application publication No. CN102502613A provides a method for directly preparing graphene by using laser irradiation silicon carbide. Although the methods all involve a laser method, the scheme is only a growth mode of graphene, and does not involve structure and composition regulation of formed graphene.
In summary, although a scheme for preparing graphene and a composite material thereof by a liquid phase method is proposed at present, no report is available about the preparation of a powder non-metal doped graphene material by a laser-induced solid phase reaction. The process scheme provided by the invention not only realizes the efficient preparation of the non-metal doped graphene material by a laser method under a solid phase condition, but also solves the problem of non-uniform powder material treatment in laser treatment, and has good innovative application prospect.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing a non-metal doped porous graphene material by laser-induced solid phase, which can be applied to various energy storage batteries or capacitor materials, and simultaneously, the process greatly shortens the preparation period of products and effectively reduces the production cost and energy consumption.
The invention adopts the following technical scheme for solving the technical problems, and the method for preparing the nonmetal-doped porous graphene material by laser-induced solid phase is characterized by comprising the following specific steps:
step S1, mixing graphene oxide powder and a non-metallic element inorganic salt compound, adding absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixed sample, and sealing and storing for later use, wherein the non-metallic element inorganic salt is one or more of ammonium fluoride, thiourea, ammonium nitrate or urea;
s2, transferring the mixed sample obtained in the step S1 into an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing an argon/hydrogen mixed gas into the opening end of the ampoule bottle, and controlling the flow rate of the mixed gas to be 10-15mL/min;
s3, placing the ampoule bottle under a laser emitter, controlling the rotating speed of a rotating motor to be 10-30rpm, adjusting the laser power of the laser emitter to be 1-10W, irradiating the mixed sample in the ampoule bottle with laser, scanning for 5-10min, and stopping laser processing;
and S4, taking down the ampoule, soaking the laser-treated sample in an acid solution, washing with deionized water, and freeze-drying to obtain the non-metal doped porous graphene material.
Further limiting, in the step S1, the graphene oxide powder is mechanically pulverized and sieved by a 200-mesh sieve in advance.
Further limiting, in the step S1, the mass ratio of the non-metallic element inorganic salt compound to the graphene oxide powder is 0.05-1.
Further, in step S2, the volume percentage of hydrogen in the argon/hydrogen mixture is 10%.
Further, the rated power of the laser emitter in step S3 is 30W, and the laser emitter emits fiber laser with a wavelength of 1064 nm.
Further, the acid solution in step S4 is 1mol/L hydrochloric acid solution.
Compared with the prior art, the invention has the following advantages and beneficial effects: the preparation method is simple and easy in operation process, good in repeatability, short in preparation period, simple and convenient in process and convenient for large-scale production, the graphene powder material is subjected to heating treatment by adopting laser, and the inside and the outside of the powder material are uniformly heated by the laser by utilizing atmosphere purging and reactor rotation in the laser heating treatment process, so that the uniform nonmetal-doped porous graphene material is formed, and meanwhile, the nitrogen-doped graphene material prepared by the preparation method is high in catalytic energy storage performance and has good stability.
Drawings
Fig. 1 is a scanning electron microscope image of the non-metal doped porous graphene material prepared in example 1.
Fig. 2 is an X-ray photoelectron spectrum of the non-metal-doped porous graphene material prepared in example 1, and it can be seen from the graph that N and S elements are doped in the material.
Fig. 3 is a graph of cyclic voltammetry performance analysis of symmetric supercapacitors made of the non-metal doped graphene materials prepared in examples 1-3 and comparative example 1.
Fig. 4 is a graph illustrating performance analysis of lithium sulfur batteries manufactured using the non-metal-doped graphene materials according to examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail below with reference to specific experiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above-described subject matter of the present invention are within the scope of the present invention.
Example 1
Step S1, mechanically pulverizing graphene oxide powder, sieving the powder through a 200-mesh sieve for later use, mixing the graphene oxide powder and thiourea according to a mass ratio of 1;
s2, transferring the obtained mixed sample to an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing an argon/hydrogen mixed gas (wherein the volume percentage of hydrogen is 10%) into the opening end of the ampoule bottle, and controlling the flow rate of the mixed gas to be 15mL/min;
s3, placing the ampoule bottle under a laser emitter, controlling the rotating speed of a rotating motor to be 20rpm, controlling the rated power of the laser emitter to be 30W, emitting fiber laser with the wavelength of 1064nm by the laser emitter, adjusting the laser power of the laser emitter to be 10W, irradiating the mixed sample in the ampoule bottle by the laser, scanning for 10min, and stopping laser processing;
and S4, taking down the ampoule, soaking the laser-treated sample in 1mol/L hydrochloric acid solution, washing with deionized water, and freeze-drying for 12 hours to obtain the non-metal doped porous graphene material.
Example 2
Step S1, mechanically powdering graphene oxide powder, sieving the powder through a 200-mesh sieve for later use, mixing the graphene oxide powder and thiourea according to the mass ratio of 1;
s2, transferring the obtained mixed sample into an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing an argon/hydrogen mixed gas (wherein the volume percentage of hydrogen is 10%) into the opening end of the ampoule bottle, and controlling the flow rate of the mixed gas to be 10mL/min;
s3, placing the ampoule bottle under a laser emitter, controlling the rotating speed of a rotating motor to be 20rpm, controlling the rated power of the laser emitter to be 30W, emitting fiber laser with the wavelength of 1064nm by the laser emitter, adjusting the laser power of the laser emitter to be 1W, irradiating the mixed sample in the ampoule bottle by the laser, scanning for 10min, and stopping laser processing;
and S4, taking down the ampoule, soaking the laser-treated sample in 1mol/L hydrochloric acid solution, washing with deionized water, and freeze-drying for 12 hours to obtain the non-metal doped porous graphene material.
Example 3
Step S1, mechanically powdering graphene oxide powder, sieving the powder through a 200-mesh sieve for later use, mixing the graphene oxide powder and thiourea according to the mass ratio of 1;
s2, transferring the obtained mixed sample to an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing an argon/hydrogen mixed gas (wherein the volume percentage of hydrogen is 10%) into the opening end of the ampoule bottle, and controlling the flow rate of the mixed gas to be 12mL/min;
s3, placing the ampoule bottle under a laser emitter, controlling the rotating speed of a rotating motor to be 20rpm, controlling the rated power of the laser emitter to be 30W, emitting fiber laser with the wavelength of 1064nm by the laser emitter, adjusting the laser power of the laser emitter to be 5W, irradiating the mixed sample in the ampoule bottle by the laser, scanning for 10min, and stopping laser processing;
and S4, taking down the ampoule bottle, soaking the sample subjected to the laser treatment in 1mol/L hydrochloric acid solution, washing with deionized water, and freeze-drying for 12 hours to obtain the non-metal doped porous graphene material.
Comparative example 1
Step S1: mechanically pulverizing graphene oxide powder, sieving the powder with a 200-mesh sieve for later use, mixing the graphene oxide powder and thiourea according to the mass ratio of 1;
step S2: transferring the obtained mixed sample to a tubular furnace, introducing argon-hydrogen mixed gas (wherein the volume percentage of the hydrogen is 10%), controlling the flow rate of the mixed gas to be 50ml/min, heating to 500 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 1h, and cooling to room temperature;
and step S3: soaking a sample in 1mol/L hydrochloric acid solution, washing with deionized water, and freeze-drying for 12h to obtain the non-metal doped porous graphene material.
The performance analysis of the super capacitor and the lithium-sulfur battery prepared from the samples prepared in comparative example 1 and example 1 can obviously find that the material performance prepared by the laser method is greatly improved compared with that prepared by the traditional thermal sintering method. Meanwhile, under different doping systems, even samples obtained by weak laser treatment such as example 2 and example 3 can obtain the non-metal doped graphene material with better performance than that prepared by the traditional thermal sintering method. Especially considering that the laser method has a time of 15min at most and a power of 10W at most, it has higher cost advantage and energy consumption advantage compared with the conventional heating method with high power.
While the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (6)
1. A method for preparing a non-metal doped porous graphene material by laser-induced solid phase is characterized by comprising the following specific steps:
step S1, mixing graphene oxide powder and a non-metal element inorganic salt compound, adding absolute ethyl alcohol, grinding and mixing uniformly to obtain a mixed sample, and sealing and storing for later use, wherein the non-metal element inorganic salt is one or more of ammonium fluoride, thiourea, ammonium nitrate or urea;
s2, transferring the mixed sample obtained in the step S1 into an ampoule bottle, fixing the ampoule bottle on a rotating motor, introducing argon/hydrogen mixed gas into the opening end of the ampoule bottle, and controlling the flow rate of the mixed gas to be 10-15mL/min;
s3, placing the ampoule bottle under a laser emitter, controlling the rotating speed of a rotating motor to be 10-30rpm, adjusting the laser power of the laser emitter to be 1-10W, irradiating the mixed sample in the ampoule bottle with laser, scanning for 5-10min, and stopping laser processing;
and S4, taking down the ampoule bottle, soaking the sample subjected to the laser treatment in an acid solution, washing with deionized water, and freeze-drying to obtain the non-metal doped porous graphene material.
2. The method for preparing the non-metal doped porous graphene material by laser-induced solid phase according to claim 1, wherein: and (2) mechanically powdering the graphene oxide powder in the step (S1) in advance, and sieving the graphene oxide powder with a 200-mesh sieve.
3. The method for preparing the non-metal doped porous graphene material by laser-induced solid phase according to claim 1, wherein: the mass ratio of the non-metallic element inorganic salt compound to the graphene oxide powder in the step S1 is 0.05-1.
4. The method for preparing the non-metal doped porous graphene material by laser-induced solid phase according to claim 1, wherein: and in the step S2, the volume percentage of hydrogen in the argon/hydrogen mixed gas is 10%.
5. The method for preparing the non-metal doped porous graphene material by laser-induced solid phase according to claim 1, wherein: and in the step S3, the rated power of the laser transmitter is 30W, and the laser transmitter transmits the fiber laser with the wavelength of 1064 nm.
6. The method for preparing the non-metal doped porous graphene material by laser-induced solid phase according to claim 1, wherein: the acid solution in the step S4 is 1mol/L hydrochloric acid solution.
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| CN103769609A (en) * | 2014-02-24 | 2014-05-07 | 中山大学 | Precious metal-semiconductor composite structure micro-nano particle, preparation method, and application |
| CN207267895U (en) * | 2017-07-19 | 2018-04-24 | 旭科新能源股份有限公司 | Industrialize the reaction liquor heating device of chemical bath method deposition film |
| CN109110751A (en) * | 2018-07-24 | 2019-01-01 | 西安交通大学 | A kind of supper-fast single or multiple element universal method of doping of graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103769609A (en) * | 2014-02-24 | 2014-05-07 | 中山大学 | Precious metal-semiconductor composite structure micro-nano particle, preparation method, and application |
| CN207267895U (en) * | 2017-07-19 | 2018-04-24 | 旭科新能源股份有限公司 | Industrialize the reaction liquor heating device of chemical bath method deposition film |
| CN109110751A (en) * | 2018-07-24 | 2019-01-01 | 西安交通大学 | A kind of supper-fast single or multiple element universal method of doping of graphene |
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