CN113060724B - Hollow carbon sphere and preparation method and application thereof - Google Patents
Hollow carbon sphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN113060724B CN113060724B CN202110325859.XA CN202110325859A CN113060724B CN 113060724 B CN113060724 B CN 113060724B CN 202110325859 A CN202110325859 A CN 202110325859A CN 113060724 B CN113060724 B CN 113060724B
- Authority
- CN
- China
- Prior art keywords
- hollow carbon
- carbon
- hollow
- spheres
- sphere
- 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.)
- Active
Links
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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a hollow carbon sphere and a preparation method and application thereof, wherein the preparation raw materials of the hollow carbon sphere comprise a carbon source and a catalyst; the carbon source comprises polytetrafluoroethylene or a combination of polytetrafluoroethylene and other carbon sources. The hollow carbon spheres have the advantages of high dispersion degree, small and uniform particle size and high graphitization degree, and have high reversible specific capacity and excellent cycling stability when being used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a hollow carbon sphere and a preparation method and application thereof.
Background
Carbon materials have been widely used as electrode materials for lithium ion batteries because of their low cost, low operating voltage, high electrical conductivity, good cycle life, and small volume change during lithium intercalation/deintercalation, and carbon materials are also used in energy fields such as sodium ion batteries, potassium ion batteries, supercapacitors, and the like.
CN110729480A discloses a nitrogen-doped porous hollow carbon sphere and a preparation method thereof, wherein the preparation method disclosed by the invention comprises the steps of obtaining melamine resin spheres through one-step condensation of melamine and formaldehyde, and coating polypyrrole on the melamine resin spheres by taking the spheres as a template, taking pyrrole as a nitrogen source and a carbon source and taking ammonium persulfate as a catalyst; and (3) gradually decomposing the melamine resin pellets in the roasting process by controlling roasting to obtain the nitrogen-doped porous hollow carbon pellets. The disclosed preparation method forms hollow carbon spheres with a large particle size.
CN112090395A discloses a method for preparing carbon cages with ultra-high dye adsorption performance by using different activating agents. The disclosed method comprises the following steps: stirring and mixing the tar, the absolute ethyl alcohol and the silicon dioxide uniformly, drying to obtain a silicon-carbon material, and then carbonizing to obtain C/SiO of the tar-carbon-coated nano silicon dioxide 2 A material; mixing C with SiO 2 Adding the materials into water, adding hydrofluoric acid, stirring and mixing uniformly, separating, and drying to obtain hollow carbon spheres; adding an activating agent into the hollow carbon spheres, adding water, uniformly stirring, drying, activating, adding the activated carbon spheres into the water, carrying out solid-liquid separation, and washing and drying the solid to obtain the carbon cage with the ultrahigh dye adsorption performance. The preparation method disclosed by the invention utilizes the effect of the activating agent on permeation, adsorption and wetting of the hollow carbon spheres to change the surface of the hollow carbon spheres, can effectively improve the specific surface area of the porous carbon cage, and further can effectively improve the adsorption performance of the porous carbon cage on the dye, but the preparation method does not utilize the activating agent to play a role in permeating, adsorbing and wetting the hollow carbon spheres to change the surface of the hollow carbon spheres, and can effectively improve the specific surface area of the porous carbon cage, so that the adsorption performance of the porous carbon cage on the dye is improved, but the preparation method does not adopt the function of the activating agentThe influence of the carbon cage particle size and the wall thickness on the adsorption efficiency is considered.
CN112265979A discloses a method for preparing a nitrogen-doped hollow carbon sphere, which uses carbon-coated titanium dioxide mesocrystal as a template, graphitizes a carbon layer at a high temperature, and further dissolves titanium dioxide inside with hydrofluoric acid to obtain the nitrogen-doped hollow carbon sphere. The prepared nitrogen-doped hollow carbon spheres have good cycling stability and rate performance, but the disclosed carbon spheres are modified from the doping angle, and the carbon spheres with smaller particle size are not formed by the method, so that the uniformity of the particle size is poorer.
In conclusion, it is important to develop a hollow carbon sphere with a small and uniform particle size.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide hollow carbon spheres, a preparation method and application thereof, wherein the hollow carbon spheres have high dispersion degree and small and uniform particle size.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hollow carbon sphere, wherein raw materials for preparing the hollow carbon sphere comprise a carbon source and a catalyst;
the carbon source comprises polytetrafluoroethylene or a combination of polytetrafluoroethylene with other carbon sources.
The hollow carbon sphere takes polytetrafluoroethylene or the combination of polytetrafluoroethylene and other carbon sources as the carbon source, the reaction is carried out in a gaseous state by utilizing the sublimation property of the polytetrafluoroethylene at low temperature, and the catalyst catalyzes the carbon source to be cracked in situ to obtain the hollow carbon sphere. The hollow carbon spheres obtained by reaction under the gaseous condition have high dispersion degree, small and uniform particle size and high graphitization degree.
Preferably, the hollow carbon spheres are spherical or spheroidal in shape.
Preferably, the particle size D50 of the hollow carbon spheres is 10-50nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm and the like.
Preferably, the wall thickness of the hollow carbon spheres is 4-10nm, such as 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, and the like.
Preferably, the catalyst comprises ferrocene and/or ferric chloride, preferably ferrocene.
The ferrocene is preferably used as the catalyst because the ferrocene can be sublimated at low temperature and can react with fluorine ions in the polytetrafluoroethylene under a gaseous reaction, so that carbon atoms are released in situ to generate the hollow carbon spheres. The hollow carbon spheres obtained by the gaseous reaction have high dispersion degree, small and uniform particle size and high graphitization degree.
Preferably, the other carbon source comprises any one of polyvinylidene fluoride, polyethylene glycol, sucrose, glucose or phenolic resin or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of polyvinylidene fluoride and polyethylene glycol, combinations of polyethylene glycol, sucrose and glucose, combinations of polyethylene glycol, sucrose, glucose and phenolic resins, combinations of polyvinylidene fluoride, polyethylene glycol, sucrose, glucose and phenolic resins, and the like.
Preferably, the molar ratio of the polytetrafluoroethylene to carbon atoms in other carbon sources is (5-100) 1, such as 5.
Preferably, the molar ratio of carbon atoms in the carbon source to iron atoms in the catalyst is (2-20) from 1, 3.
In the invention, the molar ratio of carbon atoms in the carbon source to iron atoms in the catalyst is (2-20): 1, and the obtained hollow carbon spheres have small and uniform particle size and high graphitization degree.
In a second aspect, the present invention provides a method for preparing the hollow carbon sphere of the first aspect, the method comprising the steps of: mixing a catalyst and a carbon source according to a molar ratio, transferring the mixture into a closed reactor, and then sequentially carrying out heat treatment, cooling and separation to obtain the hollow carbon spheres;
the carbon source comprises polytetrafluoroethylene or a combination of polytetrafluoroethylene and other carbon sources.
The reason for carrying out the reaction in the closed reactor is that the selected carbon source and the catalyst can be sublimated at low temperature, reactants are in a gaseous state during heat treatment, the loss of the prepared raw materials can be reduced by the closed space, the raw materials are fully reacted, and the obtained hollow carbon spheres have smaller particle size and more uniform appearance. In addition, the separation is equivalent to further purification of the hollow carbon spheres, so that the purity of the obtained hollow carbon spheres is higher.
Preferably, the method further comprises filling a protective atmosphere in the closed reactor before the heat treatment.
Preferably, the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of nitrogen and argon, a combination of argon and helium, a combination of nitrogen, argon and helium, and the like.
Preferably, the heat treatment temperature is 400-900 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃, etc.
Preferably, the heating rate of the heat treatment is 1-30 deg.C/min, such as 1 deg.C/min, 5 deg.C/min, 10 deg.C/min, 15 deg.C/min, 20 deg.C/min, 25 deg.C/min, 30 deg.C/min, and the like.
Preferably, the constant temperature time of the heat treatment is 0.5 to 12 hours, such as 0.5 hour, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours and the like.
Preferably, the separating further comprises dispersing the cooled material in a solvent.
Preferably, the solvent comprises ethanol.
Preferably, the separation comprises any one of centrifugation, standing or suction filtration or a combination of at least two thereof.
Preferably, the separating further comprises drying the solvent.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Uniformly mixing a carbon source and a catalyst according to the molar ratio of carbon atoms to iron atoms (2-20) to 1 to obtain mixed powder;
(2) Transferring the mixed powder to a closed reactor, and filling protective atmosphere;
(3) Heating the closed reactor to 400-900 ℃ at the speed of 1-30 ℃/min under the protective atmosphere, keeping the temperature for 0.5-12h, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the hollow carbon spheres and the residual mixture in ethanol, separating and drying to obtain the hollow carbon spheres.
In a third aspect, the present invention provides a lithium ion battery comprising the hollow carbon sphere of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the hollow carbon sphere has high graphitization degree, small particle size and thin wall thickness, the particle size can reach 10-50nm, the wall thickness can reach 4-10nm, and the shape is uniform. The hollow carbon sphere is used as a lithium ion battery cathode material, and the reversible specific capacity and the capacity retention rate of 200 cycles of circulation of the material are both high. The button battery prepared by using the hollow carbon spheres as a negative electrode material and a lithium sheet as a reference electrode has a reversible specific capacity of more than 342mAh/g and a capacity retention rate of more than 90% after 200 cycles.
Drawings
FIG. 1 is a transmission electron micrograph of a hollow carbon sphere according to an example.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This embodiment provides a hollow carbon sphere, and the raw materials for preparing the hollow carbon sphere include ferrocene and polytetrafluoroethylene.
The preparation method of the hollow carbon sphere comprises the following steps:
(1) Uniformly mixing polytetrafluoroethylene (purchased from alatin and with the brand number of P110094) and ferrocene according to the molar ratio of carbon atoms to iron atoms being 20;
(2) Transferring the obtained mixed powder into a closed reaction kettle, and filling argon into the reaction kettle;
(3) Carrying out heat treatment on the closed reaction kettle in an argon atmosphere, heating to 700 ℃ at the speed of 10 ℃/min, carrying out constant-temperature heat treatment for 4h, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the mixture in ethanol, centrifuging at a low speed to separate the hollow carbon spheres from the residual mixture, taking the supernatant and drying to obtain the hollow carbon spheres.
Example 2
The embodiment provides a hollow carbon sphere, and raw materials for preparing the hollow carbon sphere include ferrocene, polytetrafluoroethylene and sucrose.
The preparation method of the hollow carbon sphere comprises the following steps:
(1) Uniformly mixing polytetrafluoroethylene (purchased from alatin and with the brand number of P110094) and a mixture of ferrocene and sucrose (the molar ratio of carbon atoms is 5;
(2) Transferring the obtained mixed powder into a closed reactor, and filling nitrogen into the reaction kettle;
(3) Carrying out heat treatment on the closed reaction product in a helium atmosphere, heating to 900 ℃ at the speed of 30 ℃/min, carrying out constant-temperature heat treatment for 0.5h, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the mixture in ethanol, centrifuging at a low speed to separate the hollow carbon spheres from the residual mixture, taking the supernatant and drying to obtain the hollow carbon spheres.
Example 3
The embodiment provides a hollow carbon sphere, and raw materials for preparing the hollow carbon sphere comprise ferrocene, polytetrafluoroethylene and glucose.
The preparation method of the hollow carbon sphere comprises the following steps:
(1) Uniformly mixing a mixture of polytetrafluoroethylene (purchased from alatin and having a mark of P110094) and glucose (the molar ratio of carbon atoms is 100);
(2) Transferring the obtained mixed powder into a closed reactor, and filling nitrogen into the reaction kettle;
(3) Carrying out heat treatment on the closed reaction product in a helium atmosphere, heating to 400 ℃ at the speed of 1 ℃/min, carrying out constant-temperature heat treatment for 12h, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the mixture in ethanol, centrifuging at a low speed to separate the hollow carbon spheres from the residual mixture, taking the supernatant and drying to obtain the hollow carbon spheres.
Example 4
The embodiment provides a hollow carbon sphere, and raw materials for preparing the hollow carbon sphere include ferrocene, polytetrafluoroethylene and polyvinylidene fluoride.
The preparation method of the hollow carbon sphere comprises the following steps:
(1) Uniformly mixing a mixture (carbon atom molar ratio is 20;
(2) Transferring the obtained mixed powder into a closed reactor, and filling nitrogen into the reaction kettle;
(3) Carrying out heat treatment on the closed reaction product in a helium atmosphere, heating to 600 ℃ at the speed of 5 ℃/min, carrying out constant-temperature heat treatment for 8 hours, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the mixture in ethanol, centrifuging at low speed to separate the hollow carbon spheres from the residual mixture, and drying the supernatant to obtain the hollow carbon spheres.
Example 5
The embodiment provides a hollow carbon sphere, and raw materials for preparing the hollow carbon sphere include ferrocene, polytetrafluoroethylene, polyethylene glycol and sucrose.
The preparation method of the hollow carbon sphere comprises the following steps:
(1) Uniformly mixing a mixture of polytetrafluoroethylene (purchased from aladine and having a brand of P110094), polyethylene glycol (purchased from aladine and having a brand of P103737) and sucrose (carbon atom molar ratio is 50;
(2) Transferring the obtained mixed powder into a closed reactor, and filling nitrogen into the reaction kettle;
(3) Carrying out heat treatment on the closed reaction product in a helium atmosphere, heating to 800 ℃ at the speed of 20 ℃/min, carrying out constant-temperature heat treatment for 2 hours, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the mixture in ethanol, centrifuging at low speed to separate the hollow carbon spheres from the residual mixture, and drying the supernatant to obtain the hollow carbon spheres.
Example 6
This example differs from example 1 in that the molar ratio of carbon atoms in the polytetrafluoroethylene to iron atoms in the ferrocene is 1.
Example 7
This example differs from example 1 in that the molar ratio of carbon atoms in the polytetrafluoroethylene to iron atoms in the ferrocene is 30.
Example 8
This example is different from example 1 in that it was prepared without transferring it to a closed reaction vessel and heat-treated under an argon atmosphere, and the rest was the same as example 1.
Example 9
This example is different from example 1 in that the preparation does not include the step (4), and the rest is the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that the catalyst is ferrous sulfate in equimolar amounts and the rest is the same as example 1.
Comparative example 2
The comparative example is different from example 1 only in that the carbon source is sucrose having the same number of moles of carbon atoms, and the rest is the same as example 1.
Performance testing
The hollow carbon spheres described in examples 1 to 9 and comparative examples 1 to 2 were subjected to the following tests:
(1) Transmission electron micrograph: the morphology of the sample was observed using a high-resolution transmission electron microscope (TEM, JEM-2100F).
And (2) performing electrochemical performance test by taking the hollow carbon spheres as a lithium ion battery negative electrode material, wherein the pole piece ratio is as follows: acetylene black: polyvinylidene fluoride (mass ratio) = 10, CR2025 type coin cells were prepared with a lithium sheet as a reference electrode, and the following tests were performed:
(2) Reversible specific capacity of the material: performing constant-current charge and discharge test on the battery by adopting a LAND battery test system, wherein the voltage range is 0.01-3.0V, and the current density is 1000mA/g;
(3) Capacity retention rate at 200 cycles: a battery is subjected to constant-current charge and discharge test by adopting a LAND battery test system, the voltage range is 0.01-3.0V, the current density is 1000mA/g, and the retention rate is the ratio of the reversible specific capacity after 200 cycles to the reversible specific capacity of the first cycle.
The test results are summarized in fig. 1 and table 1.
TABLE 1
The hollow carbon spheres of embodiments 1-5 of the present invention have a particle size of 10-50nm, a wall thickness of 4-10nm, a high degree of graphitization, and a uniform morphology, as shown in fig. 1 for example. The hollow carbon sphere is used as a lithium ion battery cathode material, the reversible specific capacity and the capacity retention rate of 200 cycles of circulation are both high, the reversible specific capacity of the button battery material prepared from the hollow carbon sphere in examples 1-5 is above 342mAh/g, and the capacity retention rate of 200 cycles of circulation is above 90%.
As can be seen from the analysis of comparative example 1 and example 1, the performance of comparative example 1 is inferior to that of example 1, and the comprehensive performance of the hollow carbon spheres obtained by selecting the catalyst of the invention is proved to be better.
As can be seen from the analysis of comparative example 2 and example 1, the performance of comparative example 2 is inferior to that of example 1, and the comprehensive performance of the hollow carbon spheres obtained by using the carbon source of the invention is proved to be better.
As is clear from the analysis of examples 6 to 7 and example 1, the performance of examples 6 to 7 was inferior to that of example 1, and it was confirmed that the hollow carbon spheres obtained in the range of (2 to 20): 1 molar ratio of carbon atoms in the carbon source to iron atoms in the catalyst were more excellent in overall performance.
Analysis of example 8 and example 1 revealed that example 8 was inferior to example 1, demonstrating that the hollow carbon spheres prepared in the closed reactor had better overall properties.
Analysis of example 9 and example 1 revealed that example 9 was inferior to example 1 in performance because the hollow carbon spheres not subjected to separation contained impurities, and the overall performance of the hollow carbon spheres obtained by separating the reaction mass was better.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. The preparation method of the hollow carbon sphere is characterized by comprising the following steps: mixing a catalyst and a carbon source according to a molar ratio, transferring the mixture into a closed reactor, and then sequentially carrying out heat treatment, cooling and separation to obtain the hollow carbon spheres;
the carbon source comprises polytetrafluoroethylene or a combination of polytetrafluoroethylene with other carbon sources.
2. The method according to claim 1, wherein the hollow carbon sphere has a spherical or spheroidal shape.
3. The production method according to claim 1, wherein the particle diameter D50 of the hollow carbon sphere is 10 to 50 nm.
4. The method according to claim 1, wherein the wall thickness of the hollow carbon sphere is 4 to 10 nm.
5. The method of claim 1, wherein the catalyst comprises ferrocene and/or ferric chloride.
6. The method according to claim 1, wherein the other carbon source comprises any one or a combination of at least two of polyvinylidene fluoride, polyethylene glycol, sucrose, glucose, and phenol resin.
7. The method according to claim 1, wherein the molar ratio of the polytetrafluoroethylene to carbon atoms in the other carbon source is (5-100): 1.
8. The method according to claim 1, wherein the molar ratio of the carbon atoms in the carbon source to the iron atoms in the catalyst is (2-20): 1.
9. The method of claim 1, further comprising filling the closed reactor with a protective atmosphere prior to the heat treatment.
10. The method of claim 9, wherein the protective atmosphere comprises any one of nitrogen, argon, or helium, or a combination of at least two thereof.
11. The method of claim 1, wherein the temperature of the heat treatment is 400 to 900 ℃.
12. The production method according to claim 1, wherein the temperature increase rate of the heat treatment is 1 to 30 ℃/min.
13. The method according to claim 1, wherein the heat treatment is performed for a constant temperature of 0.5 to 12 hours.
14. The method of claim 1, further comprising dispersing the cooled material in a solvent prior to the separating.
15. The method of claim 14, wherein the solvent comprises ethanol.
16. The method according to claim 1, wherein the separation comprises any one of centrifugation, standing, or suction filtration or a combination of at least two thereof.
17. The method of claim 1, further comprising drying the solvent after the separating.
18. The method of claim 1, comprising the steps of:
(1) Uniformly mixing a carbon source and a catalyst according to the molar ratio of carbon atoms to iron atoms (2-20): 1 to obtain mixed powder;
(2) Transferring the mixed powder to a closed reactor, and filling protective atmosphere;
(3) Heating the closed reactor to 400-900 ℃ at the speed of 1-30 ℃/min under the protective atmosphere, keeping the temperature for 0.5-12h, and cooling to obtain hollow carbon spheres and a residual mixture;
(4) And dispersing the hollow carbon spheres and the residual mixture in ethanol, separating and drying to obtain the hollow carbon spheres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110325859.XA CN113060724B (en) | 2021-03-26 | 2021-03-26 | Hollow carbon sphere and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110325859.XA CN113060724B (en) | 2021-03-26 | 2021-03-26 | Hollow carbon sphere and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113060724A CN113060724A (en) | 2021-07-02 |
| CN113060724B true CN113060724B (en) | 2022-11-29 |
Family
ID=76563654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110325859.XA Active CN113060724B (en) | 2021-03-26 | 2021-03-26 | Hollow carbon sphere and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113060724B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824329A (en) * | 2022-05-20 | 2022-07-29 | 南京师范大学 | Iron-containing monatomic catalyst and application thereof |
| CN116425140A (en) * | 2023-03-16 | 2023-07-14 | 上海交通大学 | Nitrogen-doped hard carbon material, preparation method thereof and application thereof in negative electrode of sodium ion battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2297032A1 (en) * | 2008-06-10 | 2011-03-23 | National Research Council Of Canada | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
| CN102208641A (en) * | 2011-05-17 | 2011-10-05 | 广州市香港科大霍英东研究院 | Method for synthesizing Fe3O4/C lithium ion battery cathode material with hollow sphere structure by one-step process |
| CN103183341B (en) * | 2013-04-02 | 2015-04-29 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN103274385B (en) * | 2013-04-26 | 2015-08-19 | 北大先行科技产业有限公司 | A kind of lithium ion battery negative material carbon microballoon and preparation method thereof |
| CN106784865B (en) * | 2016-12-22 | 2019-06-21 | 温州大学 | A kind of nitrogen co-doped carbosphere of iron and preparation method, purposes and oxygen reduction electrode |
-
2021
- 2021-03-26 CN CN202110325859.XA patent/CN113060724B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113060724A (en) | 2021-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107394125B (en) | Manganese-doped lithium iron silicate/graphene hollow nanosphere positive electrode material and preparation method thereof | |
| CN109148847B (en) | Boron-doped modified hard carbon-coated negative electrode material with high rate performance and liquid-phase preparation method thereof | |
| CN113060724B (en) | Hollow carbon sphere and preparation method and application thereof | |
| CN109167042B (en) | Lithium-rich manganese-based positive electrode material coated with composite carbon material, preparation method of lithium-rich manganese-based positive electrode material and lithium battery | |
| CN108400297B (en) | Silicon-based lithium ion battery cathode material and preparation method thereof | |
| CN105449214A (en) | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material | |
| CN106328910B (en) | Spherical composite material of nitrogen-doped carbon material and transition metal oxide and preparation method thereof | |
| CN105460917A (en) | Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method | |
| Tien et al. | Synthesis and electrochemical characterization of carbon spheres as anode material for lithium-ion battery | |
| CN110729480A (en) | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof | |
| CN113135568A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN107151014B (en) | Biological porous carbon-based lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN112687881B (en) | Ferric oxyfluoride cathode material, preparation method thereof and lithium ion battery | |
| WO2020163864A1 (en) | Immobilized selenium in a porous carbon with the presence of oxygen, and uses in a rechargeable battery | |
| CN111668453A (en) | Flexible self-supporting positive electrode material and preparation method and application thereof | |
| CN111564610B (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
| CN113013391A (en) | Method for preparing nitrogen-doped multidimensional and hierarchical porous carbon material adaptive to sulfur anode carrier of aluminum-sulfur battery | |
| CN107492641A (en) | A kind of titanium carbide four vulcanizes three titanium composite materials and preparation method thereof | |
| CN111799098A (en) | Porous carbon/metal oxide composite material and preparation method and application thereof | |
| CN109742350B (en) | Preparation method of nitrided ferroferric oxide/graphene composite material | |
| CN108270014B (en) | Method for preparing silicon dioxide/graphene composite material by supercritical carbon dioxide fluid and application | |
| CN109473648B (en) | Silicon-carbon composite material for lithium ion battery and preparation method thereof | |
| CN112079348B (en) | Preparation method and application of graphene/MOF derived sulfide composite aerogel | |
| CN112750627B (en) | Carbon nano tube and preparation method and application thereof | |
| CN114695861A (en) | Preparation method of sulfur and nitrogen co-doped porous carbon material, prepared carbon material and application 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 |