CN112537770A - Preparation method of nitrogen-doped two-dimensional carbon nanosheet - Google Patents
Preparation method of nitrogen-doped two-dimensional carbon nanosheet Download PDFInfo
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- CN112537770A CN112537770A CN202011417274.2A CN202011417274A CN112537770A CN 112537770 A CN112537770 A CN 112537770A CN 202011417274 A CN202011417274 A CN 202011417274A CN 112537770 A CN112537770 A CN 112537770A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a preparation method of a nitrogen-doped two-dimensional carbon nanosheet, which comprises the following steps: firstly, glucose, urea and Sodium Dodecyl Benzene Sulfonate (SDBS) are ultrasonically dissolved in deionized water for hydrothermal reaction. And uniformly mixing the product with KOH in a small amount of deionized water according to a certain mass ratio, and completely drying in an oven. Finally, the temperature is increased in a gradient manner in a tubular furnace, and the activation and carbonization are carried out. And washing the product after high-temperature pyrolysis to be neutral by using hydrochloric acid and deionized water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet material. The invention has simple synthesis method, special appearance and excellent electrochemical performance, and is very suitable to be used as an electrode material and applied to the field of novel secondary batteries.
Description
Technical Field
The invention belongs to the field of electrochemistry and the technical field of new energy electronic materials, and particularly relates to a preparation method of a nitrogen-doped two-dimensional carbon nanosheet.
Background
The two-dimensional material has great potential in the aspects of energy storage and conversion, sensors and the like, and becomes a hotspot of the current material research. Among a wide variety of two-dimensional materials, the two-dimensional carbon nanomaterial has good flexibility, and the preparation method is mature and diverse, has the advantages of low production cost, good conductivity and good chemical and thermal stability, and gradually becomes a hotspot and a center of gravity of research in recent years. Lk, geim, etc. first obtained single-layer graphene by exfoliating natural graphite, and revealed a novel nanocarbon material excluding fullerene and carbon nanotubes, expanding the carbon material from zero-dimension and one-dimension to two-dimension. In this context, a two-dimensional carbon sheet is rapidly developed, and the two-dimensional carbon sheet has many excellent properties: the open surface can obviously promote the convenient contact and the rapid diffusion of the electrolyte on the surface of the active material; the high conductivity can obviously improve the mobility of electrons in the electrode material; the high thermal stability and chemical stability can greatly enhance the corrosion resistance of the active material and prolong the service life of the electrode material.
Glucose (glucose) is low in cost, and a polycondensation reaction is easy to occur at a high temperature, so that a spherical glucose polymer is obtained. And then the carbon material is formed after high-temperature pyrolysis in a tubular furnace. However, the conventional preparation method is easy to break the glucose spheres during high-temperature carbonization, and the electrochemical performance is poor. In the research, urea is introduced as a nitrogen source, an anionic surfactant is added in the reaction process, so that the micro appearance of glucose spheres is improved, the thermal stability is improved, the glucose spheres are mixed with KOH with a certain mass ratio, the glucose spheres are converted into a nitrogen-doped two-dimensional carbon sheet after activation and carbonization, and the prepared two-dimensional carbon nanosheet is good in electrochemical performance when being used as an electrode material of a lithium-sulfur battery through heteroatom doping and micro regulation and control of the surfactant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention makes full use of the high nitrogen content of urea and the microcosmic regulation and control effect of the surfactant
The preparation method of the nitrogen-doped two-dimensional carbon nanosheet with simple and convenient synthesis process and special morphology is characterized by comprising the following steps of:
(1) ultrasonically dissolving 9.0 g of glucose, 0.5 g to 2.0 g of urea and 0.2 g to 1.0 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and preserving heat for 4 to 8 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 0.25-2.0 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 ℃, preserving heat for 1-3 h, and then keeping the temperature for 2 min-1Heating to 700-800 ℃, and preserving heat for 1-3 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
According to the invention, it is preferred that in step (1) the mass of urea is 0.5455 g and the mass of SDBS is 0.2 g
According to the present invention, it is preferred that the incubation time in step (1) is 4 h.
According to the invention, it is preferred that the mass of KOH in step (2) is 1.5 g.
According to the invention, preferably, the 300 ℃ heat preservation time in the step (3) is 1 h, and the subsequent temperature rise temperature is 700 ℃.
According to the present invention, it is preferable that the holding time of the subsequent elevated temperature in the step (3) is 1 hour.
Compared with the prior art, the invention has the following technical advantages:
(1) according to the invention, urea is used as a nitrogen source, and SDBS is used as a surfactant, so that the nitrogen content of the two-dimensional carbon sheet is increased, a large number of active sites are provided, and the thermal stability of the glucose ball can be improved. The shuttle effect can be effectively relieved when the lithium sulfur battery electrode material is used as a lithium sulfur battery electrode material, the electrochemical performance of the lithium sulfur battery electrode material is excellent, and the lithium sulfur battery electrode material can be widely applied to the field of novel secondary batteries.
(2) The preparation method is simple and can be used for large-scale production.
Drawings
Fig. 1 is a scanning electron microscope image of a nitrogen-doped two-dimensional carbon sheet prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the nitrogen-doped two-dimensional carbon sheet prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
(1) ultrasonically dissolving 9.0 g of glucose, 0.5455 g of urea and 0.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and keeping the temperature for 4 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 1.5 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 deg.C, maintaining for 1 h, and then heating at 2 deg.C for 2 min-1Heating to 700 ℃, and preserving heat for 1 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
The scanning electron microscope image of the nitrogen-doped two-dimensional carbon sheet prepared by the embodiment is shown in fig. 1, and the transmission electron microscope image is shown in fig. 2, so that the product shows a large-scale two-dimensional flaky morphology from fig. 1 and 2.
Example 2:
(1) ultrasonically dissolving 9.0 g of glucose, 0.2727 g of urea and 0.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and keeping the temperature for 4 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 1.5 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 deg.C, maintaining for 1 h, and then heating at 2 deg.C for 2 min-1Heating to 700 ℃, and preserving heat for 1 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
Example 3:
(1) ultrasonically dissolving 9.0 g of glucose, 0.1363 g of urea and 0.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and keeping the temperature for 4 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 1.5 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 deg.C, maintaining for 1 h, and then heating at 2 deg.C for 2 min-1Heating to 700 ℃, and preserving heat for 1 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
Example 4:
(1) ultrasonically dissolving 9.0 g of glucose and 0.5455 g of urea in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and keeping the temperature for 4 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 1.5 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 deg.C, maintaining for 1 h, and then heating at 2 deg.C for 2 min-1Heating to 700 ℃, and preserving heat for 1 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
Example 5:
(1) ultrasonically dissolving 9.0 g of glucose, 0.5455 g of urea and 0.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and keeping the temperature for 4 hours;
(2) and (3) pumping and filtering the product by using deionized water and absolute ethyl alcohol, washing for multiple times, and then putting the product into an oven for drying. Weighing 0.5 g of black powder, uniformly mixing with 1.5 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the temperature rise condition is as follows: at 5 ℃ for min-1Heating to 700 deg.CAnd (5) warming for 3 h. And naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
Claims (7)
1. A preparation method of a nitrogen-doped two-dimensional carbon nanosheet comprises the following steps:
(1) ultrasonically dissolving 9.0 g of glucose, 0.5 g to 2.0 g of urea and 0.2 g to 1.0 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 80 ml of deionized water, carrying out hydrothermal reaction at 180 ℃, and preserving heat for 4 to 8 hours;
(2) pumping and filtering the product with deionized water and absolute ethyl alcohol, washing for multiple times, and drying in an oven; weighing 0.5 g of black powder, uniformly mixing with 0.25-2.0 g of KOH, and drying;
(3) and (3) activating and carbonizing the completely dried product at high temperature in a tubular furnace in an argon atmosphere, wherein the gradient temperature rise condition is as follows: at 5 ℃ for min-1Heating to 300 ℃, preserving heat for 1-3 h, and then keeping the temperature for 2 min-1And heating to 700-800 ℃, preserving heat for 1-3 h, naturally cooling to room temperature, washing to neutrality by using dilute hydrochloric acid and distilled water, and drying to obtain the nitrogen-doped two-dimensional carbon nanosheet.
2. A method of producing nitrogen-doped two-dimensional carbon nanoplatelets according to claim 1 wherein the mass of urea in step (1) is 0.5455 g.
3. The method for producing nitrogen-doped two-dimensional carbon nanosheets of claim 1, wherein the SDBS in step (1) has a mass of 0.2 g.
4. A method of making nitrogen-doped two-dimensional carbon nanoplatelets as in claim 1 wherein the incubation time in step (1) is 4 hours.
5. A method of making nitrogen-doped two-dimensional carbon nanoplatelets as in claim 1 wherein the mass of KOH in step (2) is 1.5 g.
6. The method for preparing nitrogen-doped two-dimensional carbon nanosheets of claim 1, wherein the pre-carbonization hold time in step (3) is 1 h.
7. The method for preparing nitrogen-doped two-dimensional carbon nanosheets according to claim 1, wherein the subsequent temperature rise in step (3) is 700 ℃ and the holding time is 1 h.
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Citations (5)
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| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| CN105314619A (en) * | 2014-08-05 | 2016-02-10 | 无锡华臻新能源科技有限公司 | Preparation method for mesoporous carbon with high nitrogen-doped content |
| WO2018067292A1 (en) * | 2016-08-19 | 2018-04-12 | Farad Power, Inc. | A method of making heteroatom-doped activated carbon |
| CN109360740A (en) * | 2018-12-17 | 2019-02-19 | 华进半导体封装先导技术研发中心有限公司 | Porous carbon nanosheet of a kind of two dimension N doping and preparation method thereof |
| US20200343054A1 (en) * | 2017-10-31 | 2020-10-29 | Gegadyne Energy Labs Pvt Ltd. | High capacitance composites |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105314619A (en) * | 2014-08-05 | 2016-02-10 | 无锡华臻新能源科技有限公司 | Preparation method for mesoporous carbon with high nitrogen-doped content |
| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| WO2018067292A1 (en) * | 2016-08-19 | 2018-04-12 | Farad Power, Inc. | A method of making heteroatom-doped activated carbon |
| US20200343054A1 (en) * | 2017-10-31 | 2020-10-29 | Gegadyne Energy Labs Pvt Ltd. | High capacitance composites |
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| WENZHONG SHEN ET AL: "Cellulose generated-microporous carbon nanosheets with nitrogen doping", 《RSC ADVANCES》 * |
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