CN114291807A - Preparation method and application of single-layer carbon nano net material - Google Patents
Preparation method and application of single-layer carbon nano net material Download PDFInfo
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a single-layer carbon nano net material, which comprises the following steps: the method comprises the following steps: pretreating a biomass raw material; step two: hydrothermally synthesizing a biomass precursor; step three: calcining and synthesizing the carbon nano-net by a sectional method. The carbon conductive frame material has stronger structural stability, better mechanical property and conductive capability, is a nanoscale carbon net with the characteristic of a fishing net in the true sense, and is not prepared by methods such as activator etching pore-forming, template-removing pore-forming, carbon fiber physical building and the like; the preparation method is simple and efficient in preparation process, uses agricultural and forestry wastes as raw materials, is low in cost and environment-friendly, and solves the problems that the existing carbon conductive net material is low in cost and cannot have high electrochemical performance; in addition, the preparation method can produce high value-added product metal Sn; the carbon nano net prepared by the invention has the characteristic of an integrally formed single-layer nano structure, and has multifunctional application.
Description
Technical Field
The invention belongs to the field of preparation of battery cathode materials and electrocatalysis materials, and particularly relates to a preparation method and application of a single-layer carbon nano net material.
Background
The carbon conductive net material has the characteristics of large specific surface area, high porosity, low cost, high physical and chemical stability and the like, and has practical application values in the fields of capacitors, electrocatalysis, electrode conductive agents, battery cathode materials and the like. The preparation method of the carbon conductive net material is various, and mainly comprises a template method, an activation method, a carbon fiber lapping method and the like.
The synthesis idea of preparing the carbon conductive mesh material by the template method is, for example, Wang et al synthesizes and prepares the boron-doped three-dimensional porous carbon mesh material by using citric acid as a carbon source and NaCl and HBO3 as templates and through the steps of freeze drying, high-temperature carbonization and template removal. And carbon conductive mesh materials such as graphene foam are also mainly constructed by a template method, for example, Yavair et al uses foam nickel as a template, deposits carbon and a layer of polymethyl methacrylate (preventing the collapse of a carbon structure) on the surface of the foam nickel by a chemical vapor deposition method, removes a nickel support by hot hydrochloric acid, dissolves the polymethyl methacrylate by hot acetone, and finally obtains the three-dimensional graphene foam mesh. Obviously, the pores of the carbon conductive net prepared by the template method are highly dependent on the size of the template, and the template material consumption is large, so that the pores can be formed by further etching by a solution method. In addition, the cost of carbon sources such as graphene is high, the total preparation method is complex, the synthesis cost is high, and the mechanical property of the product is poor.
The activation method usually uses chemical reagents to react with a carbon source in the pyrolysis process, and then a large amount of pores are etched in the carbon substrate to obtain a carbon conductive network structure, wherein the common chemical reagents include KOH, NaOH, ZnCl2, H3PO4 and the like. Biomass is used as a carbon source to prepare a porous carbon conductive mesh material, which is also common, for example, Naresh and the like, the phyllanthus emblica leaves are dried and ground into powder for pre-carbonization, then KOH solution is added for grinding, then high-temperature calcination is carried out, hydrochloric acid is used for washing and removing impurities after cooling, and a three-dimensional carbon conductive mesh is obtained after drying. In the above schemes, pores are formed on the carbon substrate by oxidizing and etching the carbon substrate at a high temperature by using chemical reagents (such as KOH and NaOH), and pores with different sizes are formed on the carbon substrate, so that the obtained carbon structure is generally a porous carbon structure with a large number of pores inside and has a single structural characteristic.
The carbon fiber lapping method, such as preparing carbon fibers by combining an electrostatic spinning technology with a high-temperature carbonization method, physically stacking the carbon fibers to form a three-dimensional carbon conductive net. For example: qu et al prepared three-dimensional carbon nanofiber networks using polyacrylonitrile and dimethylformamide, using electrospinning and heat treatment. The electrostatic spinning technology has low spinning efficiency, is usually carried out in a strong corrosive toxic solvent, has high cost, is difficult to recover, and is easy to cause environmental pollution, and a carbon net prepared by the electrostatic spinning technology is obtained by stacking carbon fibers, has poor designability and uneven pore size. Lai et al use bacterial cellulose nanofibers as raw materials, mix with CNT, ultrasonically disperse, and then prepare a CNF/CNT carbon conductive network by vacuum filtration. In the above methods, the carbon conductive mesh is built by stacking carbon fibers or carbon nanotubes, and obviously, the structural stability of the carbon mesh formed by physical stacking is poor; and the carbon nano tube and the carbon fiber have high preparation cost and are not environment-friendly, and the carbon fiber has larger diameter and is in the micro-nano grade.
At present, the carbon conductive mesh material still faces the outstanding defects of single structure, poor mechanical property, high preparation cost, complex route and the like, and the carbon nano mesh material has a larger development space no matter from the selection of a precursor, the structural design or the innovation of a preparation method. Therefore, the integrally formed carbon nano-mesh material with multiple pore channels, large specific surface area, high porosity and high structural stability is obtained by a green and low-cost synthesis method, and has important significance for the practical application of electrocatalysis, conductive agents, battery cathode materials and the like.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method and application of a single-layer carbon nano-net material, wherein etching carbon pore-forming is not needed, a mesh structure is not copied by a template method, a biomass matrix is carbonized in a self-splitting manner by a segmented heating method to form a carbon nano-net, and the prepared integrally-formed single-layer carbon nano-net has high ionic and electronic conductivity and strong structural stability.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of a single-layer carbon nano net material comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
shearing a biomass raw material, cleaning the biomass raw material with pure water, collecting the sheared biomass raw material into a container through suction filtration, putting the container into a first air-blast oven, drying and collecting the biomass raw material;
adding the dried biomass raw material into the delignification solution, putting the mixture into a second air-blowing oven for reaction, cooling the reaction temperature to room temperature, washing with water for multiple times, carrying out suction filtration to remove the residual delignification solution, drying and collecting to obtain flaky pretreated biomass rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding the activated pretreated biomass into DI water, adding a tin source and a sulfur source, stirring, transferring the mixed solution into a stainless steel high-temperature reaction kettle, and putting the stainless steel high-temperature reaction kettle into a third air-blast oven for reaction;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS-containing product2The biomass precursor of (1);
step three: calcining and synthesizing the carbon nano-net by a sectional method:
calcining the biomass precursor obtained by freeze drying in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
firstly, heating to 400-600 ℃ at the heating rate of 5-15 ℃/min and calcining for 0.5-4h to obtain the SnS/C composite material with the single-layer sheet mesh structure;
heating to 700-.
Further, the temperature of the first air blowing oven in the first step is 50-120 ℃.
Further, in the first step, the temperature of the second air-blast oven is 80-160 ℃, the reaction time is 1-7h, and the concentration of the delignification solution is 0.5-4 mol/L.
Further, the concentration of the tin source in the DI water in the second step is 0.003-0.03mol/L, and the molar ratio of the selenium source to the sulfur source is 1:2-1: 15.
Further, the stirring time in the second step is 10-40min, the temperature in the third air blast oven is 130-220 ℃, and the reaction time is 10-18 h.
Further, the biomass raw material is one of bagasse, shaddock peel and corncob.
Further, the delignification solution is one of KOH, NaOH, sodium hypochlorite and hydrogen peroxide.
Further, the tin source is SnCl4 & 5H2O, and the sulfur source is thioacetamide or thiourea.
Further, the third step specifically includes:
firstly, heating to 500 ℃ at a heating rate of 10 ℃/min and calcining for 3h to obtain the SnS/C composite material with a single-layer sheet mesh structure;
and then heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and collecting the product after cooling to obtain the single-layer carbon nano net material.
The invention also provides application of the single-layer carbon nano net material prepared by the preparation method in negative electrode materials or electrode materials of secondary batteries such as lithium/sodium/potassium/zinc ion batteries, high-performance conductive agents or capacitor electrode materials or ultrathin carrier supported catalysts.
The invention has the beneficial effects that:
1. the invention provides an integrally formed single-layer carbon nano net material with high structural stability, wherein the pore size of the nano net is about 50 nm, and the diameter of the net fiber is about 8 nm. The single-layer carbon nano-net formed by the bagasse self-splitting carbonization is integrally formed, and compared with a carbon net formed by physically stacking carbon fibers and carbon nano-tubes, the single-layer carbon nano-net has stronger structural stability and better mechanical property and electric conductivity. In addition, compared with the existing carbon conductive net material, the prepared single-layer carbon nano net material is a nano-scale carbon net with the characteristic of a fishing net in the true sense, and is not a carbon conductive frame material prepared by methods such as activator etching pore-forming, template-removing pore-forming, carbon fiber physical building and the like.
2. The preparation method disclosed by the invention is simple and efficient in preparation process, uses agricultural and forestry wastes as raw materials, is low in cost and environment-friendly, and solves the problems that the existing carbon conductive net material is low in cost and cannot have high electrochemical performance and the like. Compared with the prior art of the carbon conductive net material, the preparation process is simple and unique, the pore structure is not required to be copied by a template method, the shrinkage force of bagasse cellulose carbonization at high temperature is utilized, and the self-splitting of bagasse carbon sheets is realized to form the carbon nano net structure by combining the physical barrier effect of SnS 2. In addition, the preparation method can produce high value-added product metal Sn.
3. The carbon nano-net has the characteristic of an integrally formed single-layer nano-structure, has multifunctional application, can be directly used as a negative electrode material of a secondary battery such as a lithium/sodium/potassium/zinc ion battery, or used as a high-performance conductive agent of an electrode material and a capacitor electrode material, and can also be used as an ultrathin carrier supported catalyst to be applied to the field of electrocatalysis.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a scanning electron micrograph of the carbon nanoweb material obtained in example 1;
FIG. 2 is an X-ray diffraction spectrum of the carbon nanoweb material obtained in example 1;
FIG. 3 is a cycle performance diagram of the carbon nano-mesh material obtained in example 1 as a negative electrode material of a lithium ion battery at a current density of 0.2A/g;
fig. 4 is a cycle performance graph of the carbon nanoweb material obtained in example 1 as a negative electrode material of a sodium ion battery at a current density of 0.2A/g.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a single-layer carbon nano net material comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
cutting bagasse, cleaning with pure water, collecting the cut bagasse into a container through suction filtration, drying in a first air-blast oven, and collecting, wherein the temperature of the first air-blast oven is 60 ℃;
adding the dried bagasse into a KOH-removed solution with the concentration of 1mol/L, placing the bagasse into a second air-blowing oven for reaction, wherein the temperature of the second air-blowing oven is 110 ℃, the reaction time is 3 hours, removing lignin and hemicellulose in the bagasse, retaining cellulose, reducing the reaction temperature to room temperature, washing with water for multiple times, carrying out suction filtration to remove residual KOH, drying, and collecting the flaky pretreated bagasse rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding activated pretreated bagasse into DI water, adding SnCl4 & 5H2O and thioacetamide, wherein the concentration of SnCl4 & 5H2O in the DI water is 0.01 mol/L, the molar ratio of SnCl4 & 5H2O to thioacetamide is 1:5, stirring for 30min, transferring the mixed solution into a stainless steel high-temperature reaction kettle, and putting the stainless steel high-temperature reaction kettle into a third forced air oven for reaction, wherein the temperature in the third forced air oven is 160 ℃, and the reaction time is 12H;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS2A bagasse precursor; SnS2Generated inside the flaky bagasse to be the physical barrier between bagasse cellulose nano-beams;
step three: calcining and synthesizing the carbon nano-net by a sectional method:
SnS obtained by freeze drying2The bagasse precursor is calcined in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
heating to 500 ℃ at a heating rate of 10 ℃/min and calcining for 3h, carbonizing and shrinking the cellulose of the bagasse at high temperature, and simultaneously, because of SnS2The bagasse carbon sheet is self-split to form a primary carbon net structure; in addition, because the carbon generated by bagasse under the oxygen-free high-temperature condition has reducibility, SnS is generated in the calcining process2The bagasse can be reduced into SnS, and the SnS/C composite material with a single-layer sheet mesh structure is obtained;
heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, cooling, and collecting the product to obtain the single-layer carbon nano net material; SnS is reduced into Sn under the reducing action of carbon in the temperature rising process, and Sn can be completely gasified and volatilized after heat preservation for 2 h.
Example 2:
a preparation method of a single-layer carbon nano net material comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
cutting bagasse, cleaning with pure water, collecting the cut bagasse into a container through suction filtration, drying in a first air-blast oven, and collecting, wherein the temperature of the first air-blast oven is 50 ℃;
adding the dried bagasse into a NaOH-removing solution with the concentration of 0.5mol/L, placing the bagasse into a second air-blowing oven for reaction, wherein the temperature of the second air-blowing oven is 80 ℃, the reaction time is 1h, after the reaction temperature is reduced to room temperature, washing and filtering for multiple times to remove residual NaOH, drying and collecting the flaky pretreated bagasse rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding activated pretreated bagasse into DI water, adding SnCl4 & 5H2O and thiourea, wherein the concentration of SnCl4 & 5H2O in the DI water is 0.003 mol/L, the molar ratio of SnCl4 & 5H2O to thiourea is 1:2, transferring the mixed solution into a stainless steel high-temperature reaction kettle after stirring for 10min, and putting the stainless steel high-temperature reaction kettle into a third forced air oven for reaction, wherein the temperature in the third forced air oven is 130 ℃, and the reaction time is 10H;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS2A bagasse precursor;
step three: calcining and synthesizing the carbon nano-net by a sectional method:
SnS obtained by freeze drying2The bagasse precursor is calcined in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
firstly, heating to 400 ℃ at the heating rate of 5 ℃/min and calcining for 0.5h to obtain the SnS/C composite material with the single-layer sheet mesh structure;
heating to 700 ℃ at the heating rate of 3 ℃/min, preserving the heat for 0.5h, cooling, and collecting the product to obtain the single-layer carbon nano net material.
Example 3:
a preparation method of a single-layer carbon nano net material comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
cutting bagasse, cleaning with pure water, collecting the cut bagasse into a container through suction filtration, drying in a first air-blast oven, and collecting, wherein the temperature of the first air-blast oven is 120 ℃;
adding the dried bagasse into a sodium hypochlorite solution with the concentration of 4mol/L, placing the bagasse into a second air-blowing oven for reaction, wherein the temperature of the second air-blowing oven is 160 ℃, the reaction time is 7 hours, after the reaction temperature is reduced to room temperature, washing with water for many times, carrying out suction filtration to remove residual sodium hypochlorite, drying and collecting the flaky pretreated bagasse rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding activated pretreated bagasse into DI water, adding SnCl4 & 5H2O and thioacetamide, wherein the concentration of SnCl4 & 5H2O in the DI water is 0.03mol/L, the molar ratio of SnCl4 & 5H2O to thioacetamide is 1:15, stirring for 40min, transferring the mixed solution into a stainless steel high-temperature reaction kettle, and putting the stainless steel high-temperature reaction kettle into a third forced air oven for reaction, wherein the temperature in the third forced air oven is 220 ℃, and the reaction time is 18H;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS2A bagasse precursor;
step three: calcining and synthesizing the carbon nano-net by a sectional method:
SnS obtained by freeze drying2The bagasse precursor is calcined in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
firstly, heating to 600 ℃ at a heating rate of 15 ℃/min and calcining for 4h to obtain the SnS/C composite material with a single-layer sheet mesh structure;
and then heating to 900 ℃ at the heating rate of 7 ℃/min, preserving the heat for 3h, and collecting the product after cooling to obtain the single-layer carbon nano net material.
Example 4:
a preparation method of a single-layer carbon nano net material comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
cutting bagasse, cleaning with pure water, collecting the cut bagasse into a container through suction filtration, drying in a first air-blast oven, and collecting, wherein the temperature of the first air-blast oven is 80 ℃;
adding the dried bagasse into a hydrogen peroxide solution with the concentration of 2mol/L, placing the mixture into a second air-blowing oven for reaction, wherein the temperature of the second air-blowing oven is 120 ℃, the reaction time is 5 hours, after the reaction temperature is reduced to room temperature, washing with water for many times, carrying out suction filtration to remove residual hydrogen peroxide, drying and collecting the obtained flake-shaped pretreated bagasse rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding activated pretreated bagasse into DI water, adding SnCl4 & 5H2O and thioacetamide, wherein the concentration of SnCl4 & 5H2O in the DI water is 0.02 mol/L, the molar ratio of SnCl4 & 5H2O to thioacetamide is 1:10, transferring the mixed solution into a stainless steel high-temperature reaction kettle after stirring for 40min, and putting the stainless steel high-temperature reaction kettle into a third forced air oven for reaction, wherein the temperature in the third forced air oven is 200 ℃, and the reaction time is 18H;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS2A bagasse precursor;
step three: calcining and synthesizing the carbon nano-net by a sectional method:
SnS obtained by freeze drying2The bagasse precursor is calcined in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
firstly, heating to 500 ℃ at a heating rate of 10 ℃/min and calcining for 3h to obtain the SnS/C composite material with a single-layer sheet mesh structure;
and then heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and collecting the product after cooling to obtain the single-layer carbon nano net material.
As shown in fig. 1, a scanning electron microscope image of the carbon nanoweb material obtained in example 1 shows that it has a single-layer carbon nanoweb structure, with nanoweb pores of about 50 nm and web fiber diameters of about 8 nm; as shown in FIG. 2, the X-ray diffraction spectrum of the carbon nanoweb material obtained in example 1 is pure phase amorphous carbon (PDF # 012-0212).
And (3) testing the battery performance:
the carbon nanoweb material obtained in example 1 was mixed with a polyvinylidene fluoride (PVDF) binder in a ratio of 9: mixing the raw materials according to a mass ratio of 1, taking methyl pyrrolidone (NMP) as a solvent, mixing the raw materials to prepare slurry, coating the slurry on a metal copper foil, and drying the slurry in a vacuum drying oven at 110 ℃ for 10 hours to obtain the carbon nano-net material electrode.
CR2025 coin cells were assembled using the working electrodes described above. Assembling the lithium ion battery: lithium sheet is taken as a counter electrode, Polyethylene (PE) is taken as a diaphragm, and LiPF is taken6A1.0 mol/L solution of Propylene Carbonate (PC) was used as an electrolyte, and the assembly of the CR2016 cell was completed in a glove box under an argon atmosphere. Assembling the sodium-ion battery: sodium sheet as counter electrode, glass microfiber (Whatman, GF/A) as diaphragm, and NaClO4The assembly of the CR2025 cell was completed in a glove box under argon atmosphere using a 1.0 mol/L solution of Propylene Carbonate (PC) as the electrolyte.
The cycling performance was tested by the Land CT2001A battery test system (0.01V-3.0V) at 25 ℃.
Fig. 3 is a cycle performance diagram of the carbon nano-mesh material prepared in example 1 of the present invention as a negative electrode of a lithium ion battery at a current density of 0.2A/g. The discharge capacity is 360 mAh/g, and the coulombic efficiency reaches 99.9 percent. The material has good cycling stability and high specific discharge capacity, and is an excellent high-performance lithium ion battery cathode material.
Fig. 4 is a graph of the cycle performance of the carbon nanoweb material prepared in example 1 of the invention as a negative electrode of a sodium ion battery at a current density of 0.2A/g. The discharge capacity is 170 mAh/g, and the coulombic efficiency reaches 99.7 percent. The material has good cycling stability and high specific discharge capacity, and is an excellent high-performance sodium ion battery cathode material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a single-layer carbon nano net material is characterized by comprising the following steps: the preparation method comprises the following steps:
the method comprises the following steps: pretreatment of biomass raw materials:
shearing a biomass raw material, cleaning the biomass raw material with pure water, collecting the sheared biomass raw material into a container through suction filtration, putting the container into a first air-blast oven, drying and collecting the biomass raw material;
adding the dried biomass raw material into the delignification solution, putting the mixture into a second air-blowing oven for reaction, cooling the reaction temperature to room temperature, washing with water for multiple times, carrying out suction filtration to remove the residual delignification solution, drying and collecting to obtain flaky pretreated biomass rich in cellulose;
step two: hydrothermal synthesis of a biomass precursor:
adding the activated pretreated biomass into DI water, adding a tin source and a sulfur source, stirring, transferring the mixed solution into a stainless steel high-temperature reaction kettle, and putting the stainless steel high-temperature reaction kettle into a third air-blast oven for reaction;
cooling to room temperature, centrifuging with DI water, ultrasonically dispersing with ultrasonic machine, and freeze drying to obtain SnS-containing product2The biomass precursor of (1);
step three: calcining and synthesizing the carbon nano-net by a sectional method:
calcining the biomass precursor obtained by freeze drying in a tube furnace by a sectional method in the atmosphere of high-purity argon or nitrogen:
firstly, heating to 400-600 ℃ at the heating rate of 5-15 ℃/min and calcining for 0.5-4h to obtain the SnS/C composite material with the single-layer sheet mesh structure;
heating to 700-.
2. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the temperature of the first air-blast oven in the first step is 50-120 ℃.
3. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: in the first step, the temperature of the second air-blast oven is 80-160 ℃, the reaction time is 1-7h, and the concentration of the delignification solution is 0.5-4 mol/L.
4. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: in the second step, the concentration of the tin source in the DI water is 0.003-0.03mol/L, and the molar ratio of the selenium source to the sulfur source is 1:2-1: 15.
5. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the stirring time in the step two is 10-40min, the temperature in the third air-blast oven is 130-220 ℃, and the reaction time is 10-18 h.
6. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the biomass raw material is one of bagasse, shaddock peel and corncob.
7. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the delignification solution is one of KOH, NaOH, sodium hypochlorite and hydrogen peroxide.
8. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the tin source is SnCl4 & 5H2O, and the sulfur source is thioacetamide or thiourea.
9. The method for preparing a single-layer carbon nanomesh material of claim 1, wherein the method comprises the steps of: the third step specifically comprises:
firstly, heating to 500 ℃ at a heating rate of 10 ℃/min and calcining for 3h to obtain the SnS/C composite material with a single-layer sheet mesh structure;
and then heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and collecting the product after cooling to obtain the single-layer carbon nano net material.
10. Use of the single-layer carbon nanomesh material prepared by the preparation method of any one of claims 1 to 9 in a secondary battery negative electrode material or an electrode material high-performance conductive agent or a capacitor electrode material or an ultrathin supported catalyst.
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| CN103696239A (en) * | 2013-12-05 | 2014-04-02 | 西安航空制动科技有限公司 | Preparation method of carbon nano-fiber film |
| CN109546139A (en) * | 2019-01-07 | 2019-03-29 | 合肥学院 | A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material |
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| CN103696239A (en) * | 2013-12-05 | 2014-04-02 | 西安航空制动科技有限公司 | Preparation method of carbon nano-fiber film |
| CN109546139A (en) * | 2019-01-07 | 2019-03-29 | 合肥学院 | A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material |
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