CN112661137A - Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery - Google Patents
Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery Download PDFInfo
- Publication number
- CN112661137A CN112661137A CN202011550559.3A CN202011550559A CN112661137A CN 112661137 A CN112661137 A CN 112661137A CN 202011550559 A CN202011550559 A CN 202011550559A CN 112661137 A CN112661137 A CN 112661137A
- Authority
- CN
- China
- Prior art keywords
- soluble
- salt
- porous carbon
- metal salt
- soluble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of preparation of nano carbon materials, in particular to a porous carbon sphere, a preparation method and application in a lithium-sulfur battery. The preparation method comprises the following steps: mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound; mixing a metal organic framework compound, a soluble polymer and methanol, and then sequentially carrying out aerogel spraying treatment and carbonization to obtain porous carbon spheres; the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt. The porous carbon spheres prepared by the preparation method are assembled into secondary particles from the hollow primary particles, have the advantages of high specific surface area, hierarchical pore structure, high conductivity and the like, and show good electrochemical performance; the preparation method is high in controllability, low in cost and environment-friendly, and solves the problems that a template agent in the traditional template method is difficult to remove and the appearance of primary particles is uncontrollable.
Description
Technical Field
The invention relates to the technical field of preparation of nano carbon materials, in particular to a porous carbon sphere, a preparation method thereof and application thereof in a lithium-sulfur battery.
Background
In recent years, porous carbon spheres have attracted much attention in many application fields such as electrochemical energy storage, catalysis, drug release and adsorption because of their advantages such as large specific surface area, good electronic conductivity, low ion diffusion resistance, high tap density, and excellent chemical/electrochemical stability. When the hierarchical porous carbon sphere material is used as an electrode material of an electrochemical energy storage device, the loss of active substances can be effectively inhibited, the volume change caused by charge and discharge is adapted, the loss of the electrode material is prevented, and the electrochemical performance of the energy storage device is effectively improved.
The template method is a common method for preparing the porous carbon sphere material at present. The template method can be divided into a soft template method and a hard template method, wherein the soft template method utilizes a surfactant to react with a raw material to form a carbon precursor, and the hard template method is to remove the template by self-assembly of a ready-made spherical template material and the carbon precursor material and then acid and alkali etching. Although both methods can realize the preparation of the porous carbon material, the template removal in the preparation process is difficult and the appearance of primary particles is uncontrollable.
Disclosure of Invention
The invention aims to provide a porous carbon sphere, a preparation method thereof and application of the porous carbon sphere in a lithium-sulfur battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of porous carbon spheres, which comprises the following steps:
mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound;
mixing the metal organic framework compound, the soluble polymer and methanol, and then sequentially carrying out aerogel spraying treatment and carbonization to obtain the porous carbon spheres;
the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt.
Preferably, the concentration of the methanol solution of the soluble metal salt is 0.05-1 mol/L.
Preferably, the soluble metal salt in the methanol solution of the soluble metal salt further comprises other soluble metal salts;
the other soluble metal salt comprises one or more of soluble cobalt salt, soluble nickel salt, soluble iron salt and soluble manganese salt.
Preferably, when the soluble metal salt comprises a soluble zinc salt and other soluble metal salts, the molar ratio of the soluble zinc salt to the other soluble metal salts is (9-20): 1.
preferably, the concentration of the methanol solution of the organic ligand is 0.4-2 mol/L;
the organic ligand in the methanol solution of the organic ligand comprises imidazole organic matters and/or benzoic acid organic matters;
the molar ratio of the soluble metal salt in the methanol solution of the soluble metal salt to the organic ligand in the methanol solution of the organic ligand is 1 (1-6).
Preferably, the soluble polymer comprises one or more of ethylene oxide polymer and polyvinyl alcohol polymer;
the concentration of the soluble polymer in the mixed solution obtained by mixing the metal organic framework compound, the soluble polymer and methanol is 0.1-2 mg/mL.
Preferably, the temperature of the aerogel spray treatment is 300-800 ℃.
Preferably, the carbonization process is as follows: heating to 300 ℃ at a heating rate of 1-10 ℃/min, and then preserving heat for 1-10 h; and then heating to 900-1200 ℃ at the heating rate of 1-3 ℃/min, and preserving the heat for 3-10 h.
The invention also provides the porous carbon spheres prepared by the preparation method in the technical scheme.
The invention also provides application of the porous carbon spheres in the technical scheme in a lithium-sulfur battery.
The invention provides a preparation method of porous carbon spheres, which comprises the following steps: mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound; mixing the metal organic framework compound, the soluble polymer and methanol, and then sequentially carrying out aerogel spraying treatment and carbonization to obtain the porous carbon spheres; the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt. According to the invention, intermolecular interaction can occur between the metal organic framework compound prepared from the soluble metal salt and the organic ligand and the soluble polymer, so that the soluble polymer is adsorbed on the surface of the metal organic framework compound. In the process of aerogel spraying treatment, a solvent is volatilized to induce the aerogel to perform sound production self-assembly, so that a carbon precursor material is prepared, and then a metal organic framework compound is converted into hollow nitrogen-doped amorphous carbon through carbonization; and the metal volatilizes to cause a large amount of mesopores and micropores in the carbon spheres, thereby forming porous carbon spheres.
Compared with the prior art, the preparation method has the following beneficial effects:
1) the porous carbon spheres prepared by the preparation method are assembled by hollow carbon particles, have the advantages of high specific surface area, hierarchical pore structure, high conductivity and the like, and show good electrochemical performance when assembled into an electrochemical energy storage device;
2) the preparation method is high in controllability, low in cost and environment-friendly, and solves the problems that a template agent in the traditional template method is difficult to remove and the appearance of primary particles is uncontrollable.
Drawings
Fig. 1 is an XRD pattern of the porous carbon sphere prepared in example 1;
FIG. 2 is SEM photographs of porous carbon spheres prepared in example 1 at different magnifications;
fig. 3 is an XRD pattern of the porous carbon sphere prepared in example 1;
FIG. 4 is SEM photographs of porous carbon spheres prepared in example 2 at different magnifications;
FIG. 5 is TEM photographs of porous carbon spheres prepared in example 2 at different magnifications;
FIG. 6 is a graph showing the adsorption-desorption curves and the pore size distribution of the porous carbon spheres prepared in example 2;
FIG. 7 is a cycle life curve of a lithium sulfur battery prepared from the porous carbon spheres described in example 2;
fig. 8 is an SEM image of the carbon material prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of porous carbon spheres, which comprises the following steps:
mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound;
mixing the metal organic framework compound, the soluble polymer and methanol, and then sequentially carrying out aerogel spraying treatment and carbonization to obtain the porous carbon spheres;
the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
Mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound; the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt.
In the invention, the concentration of the methanol solution of the soluble metal salt is preferably 0.05-1 mol/L, more preferably 0.2-0.63 mol/L, and most preferably 0.3-0.5 mol/L. In the present invention, the soluble metal salt in the methanol solution of the soluble metal salt includes a soluble zinc salt; the soluble zinc salt is preferably one or more of zinc nitrate, zinc acetate, zinc sulfate and zinc chloride; when the soluble zinc salt is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the present invention, the soluble zinc salt preferably further comprises other soluble metal salts; the other soluble metal salt preferably comprises one or more of soluble cobalt salt, soluble nickel salt, soluble iron salt and soluble manganese salt; when the other soluble metal salts are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. The specific types of the soluble cobalt salt, the soluble nickel salt, the soluble iron salt and the soluble manganese salt are not limited in any way, and the types of the soluble cobalt salt, the soluble nickel salt, the soluble iron salt and the soluble manganese salt which are well known to those skilled in the art can be adopted.
In the invention, when the soluble metal salt is soluble zinc salt, the prepared porous carbon spheres are porous carbon spheres without metal element doping; when the soluble metal salt is soluble zinc salt and other soluble metal salts, the prepared porous carbon spheres are porous carbon spheres doped with metal elements; the metal element is a corresponding metal element in the other soluble metal salt.
In the invention, when the soluble metal salt comprises a soluble zinc salt and other soluble metal salts, the molar ratio of the soluble zinc salt to the other soluble metal salts is preferably (9-20): 1, more preferably (10 to 16): 1.
in the present invention, the methanol solution of the soluble metal salt is preferably prepared by dissolving the soluble metal salt in methanol.
In the invention, the concentration of the methanol solution of the organic ligand is preferably 0.4-2 mol/L, more preferably 0.6-1.8 mol/L, and most preferably 0.8-1.2 mol/L. In the invention, the organic ligand in the methanol solution of the organic ligand preferably comprises imidazole organic matters and/or benzoic acid organic matters, and more preferably comprises imidazole organic matters; the imidazole organic matter is preferably one or more of imidazole, 1-methylimidazole, 1-ethylimidazole and benzimidazole; the benzoic acid organic matter is preferably benzoic acid and/or terephthalic acid; when the organic ligands are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
In the present invention, the methanol solution of the organic ligand is preferably prepared by dissolving the organic ligand in methanol.
In the invention, when the soluble metal salt is a soluble zinc salt, the organic ligand is more preferably 2-methylimidazole, and the prepared metal organic framework compound is a ZIF-8 metal organic framework compound; when the soluble metal salt is soluble zinc salt and other soluble metal salts, the organic ligand is more preferably 2-methylimidazole, and the prepared metal organic framework compound is a bimetallic ZIF metal organic framework compound or a polymetallic ZIF metal organic framework compound.
In the present invention, the molar ratio of the soluble metal salt in the methanol solution of the soluble metal salt to the organic ligand in the methanol solution of the organic ligand is preferably 1: (1 to 6), more preferably 1: (2-5), most preferably 1: (3-4).
The mixing of the methanolic solution of the soluble metal salt and the methanolic solution of the organic ligand according to the present invention is preferably carried out under stirring conditions, and the stirring rate according to the present invention is not particularly limited, and may be carried out at a rate well known to those skilled in the art. The stirring time is preferably 10 s-10 min, and more preferably 2-6 min.
In the invention, the coordination bond self-assembly reaction is preferably carried out under a standing condition, and the standing time is preferably 12-24 h, and more preferably 16-19 h; the temperature of the standing is preferably room temperature.
After the coordination bond self-assembly reaction is completed, the invention also preferably comprises centrifugation and washing which are sequentially carried out; the centrifugation process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the washing is preferably 3 times with methanol.
After the metal organic framework compound is obtained, the metal organic framework compound, the soluble polymer and methanol are mixed, and then aerogel spraying treatment and carbonization are sequentially carried out to obtain the porous carbon ball.
In the present invention, the soluble polymer preferably includes one or more of an ethylene oxide polymer and a polyvinyl alcohol polymer; the ethylene oxide-based polymer is preferably polyethylene oxide; the polyvinyl alcohol polymer is preferably polyvinylpyrrolidone, and more preferably polyvinylpyrrolidone K90. When the soluble polymer is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the soluble polymer can be mixed according to any proportion.
In the present invention, the concentration of the soluble polymer in the mixed solution obtained by the mixing is preferably 0.1 to 2mg/mL, and more preferably 0.2 to 0.6 mg/mL.
In the present invention, the mixing preferably includes sonication and stirring, which are performed sequentially. The invention does not have any special limitation on the frequency of the ultrasound, and the ultrasound is carried out by adopting the ultrasonic frequency well known by the technical personnel in the field; the ultrasonic time is preferably 1-5 h, and more preferably 2-4 h. The stirring rate is not particularly limited in the present invention, and may be a rate well known to those skilled in the art; the stirring time is preferably 2-12 h, and more preferably 6-10 h.
In the invention, the temperature of the aerogel spray treatment is preferably 300-800 ℃, and more preferably 400-600 ℃. In the invention, in the process of aerogel spray treatment, a methanol solvent is volatilized, and a metal organic framework compound and a polymer are induced to shrink and be assembled into a sphere, so that the carbon precursor material is obtained. The obtained spherical precursor can ensure that the material can not collapse and agglomerate in the subsequent carbonization process.
In the present invention, the carbonization is preferably performed in a protective atmosphere, and the protective atmosphere is not particularly limited in the present invention, and a protective atmosphere known to those skilled in the art may be used. In the practice of the inventionIn the examples, the protective atmosphere is specifically N2An atmosphere.
In the present invention, the carbonization process is preferably: heating to 300 ℃ at a heating rate of 1-10 ℃/min, and then preserving heat for 1-10 h; heating to 900-1200 ℃ at the heating rate of 1-3 ℃/min, and preserving heat for 3-10 h; more preferably, the temperature is raised to 300 ℃ at a heating rate of 5 ℃/min, then the temperature is maintained for 2h, and then the temperature is raised from 300 ℃ to 900 ℃ at a heating rate of 2 ℃/min, and the temperature is maintained for 9 h.
In the invention, in the process of gradually raising the temperature of the carbon precursor material obtained after the aerogel spraying treatment, under two acting forces, namely an interaction force between a soluble polymer and a metal-organic framework compound and a contraction force of the metal-organic framework compound, the metal-organic framework compound can be converted into hollow amorphous carbon. When the temperature is continuously increased to 900-1200 ℃, zinc can be exerted, and a large number of mesopores and micropores are formed in the carbon spheres. When other soluble metal salts are contained, the corresponding metals in the other soluble metal salts can be converted into metal single atoms to be embedded in the carbon material, so that the transition metal doped porous carbon sphere material is formed.
After the carbonization is completed, the invention also preferably includes temperature reduction, and the temperature reduction is not limited in any way by the invention and can be reduced to room temperature by adopting a manner well known to those skilled in the art.
The invention also provides the porous carbon spheres prepared by the preparation method in the technical scheme. In the invention, the particle size of the carbon spheres is preferably 200-1500 nm; the carbon sphere is preferably assembled by a plurality of hollow polyhedral carbon particles, and the wall thickness of the hollow polyhedral carbon particles is preferably 4 nm.
The invention also provides application of the porous carbon spheres in the technical scheme in a lithium-sulfur battery. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following examples are provided to illustrate the preparation method of the porous carbon spheres of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 2.38g of zinc nitrate hexahydrate in 160mL of methanol to obtain a methanol solution of zinc nitrate;
dissolving 2.63g of dimethylimidazole in 80mL of methanol to obtain a methanol solution of dimethylimidazole;
mixing and stirring the methanol solution of zinc nitrate and the methanol solution of dimethyl imidazole for 6min, standing at room temperature for 24h, centrifuging, and washing with methanol for 3 times to obtain a metal organic framework compound;
mixing the metal organic framework compound, 0.25g of polyvinylpyrrolidone and 250mL of methanol, performing ultrasonic treatment for 3 hours, and stirring for 5 hours; then spraying aerogel at 600 ℃, and then spraying the aerogel in N2Carbonizing in the atmosphere, heating to 300 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, heating from 300 ℃ to 900 ℃ at the heating rate of 2 ℃/min, preserving heat for 9h, and cooling to room temperature to obtain the porous carbon spheres;
XRD (X-ray diffraction) testing is carried out on the porous carbon sphere, the testing result is shown in figure 1, and as can be seen from figure 1, the obtained carbon material is in an amorphous structure, and a characteristic diffraction peak of metal zinc is not observed, which indicates that the metal zinc is completely removed;
SEM test is carried out on the porous carbon spheres, the test result is shown in figure 2, and as can be seen from figure 2, the obtained material is spherical, and the size of the carbon spheres is 200-1500 nm.
Example 2
2.18g of zinc nitrate hexahydrate and 0.19g of cobalt nitrate hexahydrate are dissolved in 160mL of methanol to obtain a methanol solution of soluble metal salts;
dissolving 2.63g of dimethylimidazole in 80mL of methanol to obtain a methanol solution of dimethylimidazole;
mixing and stirring the methanol solution of the soluble metal salt and the methanol solution of the dimethyl imidazole for 6min, standing for 24h at room temperature, centrifuging, and washing for 3 times by using methanol to obtain a metal organic framework compound;
mixing the metal organic framework compound, 0.25g of polyvinylpyrrolidone and 250mL of methanol, performing ultrasonic treatment for 3 hours, and stirring for 5 hours; then carrying out air condensation at 600 DEG CAfter the glue is sprayed, at N2Carbonizing in the atmosphere, heating to 300 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, heating from 300 ℃ to 900 ℃ at the heating rate of 2 ℃/min, and preserving heat for 9h to obtain the porous carbon spheres;
XRD (X-ray diffraction) testing is carried out on the porous carbon sphere, the testing result is shown in figure 3, and as can be seen from figure 3, the obtained carbon material is in an amorphous structure, and characteristic diffraction peaks of metal zinc and cobalt are not observed, which shows that the metal zinc is completely removed, and the metal cobalt exists in a monodisperse form;
SEM test is carried out on the porous carbon spheres, the test result is shown in figure 4, and the carbon material obtained from figure 4 is spherical, and the size of the carbon spheres is 200-1500 nm.
The porous carbon spheres were subjected to TEM testing, and the test results are shown in fig. 5, from which it can be seen from fig. 5 that the carbon spheres are assembled from a plurality of hollow polyhedral carbon particles, and the thickness of the carbon wall of the hollow polyhedral carbon particles is about 4 nm.
Subjecting the porous carbon spheres to isothermal N2An adsorption-desorption test, wherein the test result is shown in fig. 6, wherein a is an adsorption-desorption curve, and b is an aperture distribution diagram; as can be seen from FIG. 6, the specific surface area and pore volume of the carbon spheres are 1150m2·g-1And 0.76cm3·g-1The pore size is mainly concentrated in micropores and 5.5nm mesopores.
Comparative example 1
2.18g of zinc nitrate hexahydrate and 0.19g of cobalt nitrate hexahydrate are dissolved in 160mL of methanol to obtain a methanol solution of soluble metal salts;
dissolving 2.63g of dimethylimidazole in 80mL of methanol to obtain a methanol solution of dimethylimidazole;
mixing and stirring the methanol solution of the soluble metal salt and the methanol solution of the dimethyl imidazole for 6min, standing for 24h at room temperature, centrifuging, and washing for 3 times by using methanol to obtain a metal organic framework compound;
in N2Carbonizing in the atmosphere, heating to 300 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, heating from 300 ℃ to 900 ℃ at the heating rate of 2 ℃/min, preserving heat for 9h, and cooling to room temperature to obtain a carbon material;
the carbon material is subjected to SEM test, the test result is shown in FIG. 8, and as can be seen from FIG. 8, the carbon material is in a solid polyhedral shape, and no hollow or spherical shape is observed.
Test example
And (2) fully grinding 40mg of the porous carbon spheres prepared in example 2 and 60mg of elemental sulfur powder in an agate mortar, then filling the ground powder into a sealed reaction container, keeping the temperature at 155 ℃ for 10 hours, and naturally cooling to room temperature to obtain the sulfur-loaded porous carbon spheres, wherein the name of the sulfur-loaded porous carbon spheres is porous carbon spheres/sulfur. The prepared porous carbon sphere/sulfur composite material is selected to prepare the lithium-sulfur battery anode, and the anode is prepared according to the following steps of: conductive carbon black: polyvinylidene fluoride (PVDF) was prepared at a mass ratio of 80:10:10 to prepare an electrode. The 2032 button cell is assembled by taking metal lithium as a cathode, and the electrolyte comprises the following components: DOL DME 1:1, 1M LiTFSI, 0.1M LiNO3. The current of the constant current charge and discharge test is 0.5C (837mA/g), and the voltage range is 1.7-3V (vs Li)+/Li). The test results are shown in fig. 7, and fig. 7 is a cycle life curve of a lithium sulfur battery prepared from the porous carbon spheres described in example 2.
As can be seen from fig. 7, the first discharge capacity of the lithium-sulfur battery prepared from the porous carbon spheres described in example 2 at 0.1C current density was 1199mAh/g, the discharge capacity at 1C current density was 1095mAh/g, the specific capacity remained 884mAh/g after 600 cycles of cycling, and the lithium-sulfur battery had high coulombic efficiency and exhibited excellent cycling stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the porous carbon spheres is characterized by comprising the following steps:
mixing a methanol solution of soluble metal salt and a methanol solution of an organic ligand to perform coordination bond self-assembly reaction to obtain a metal organic framework compound;
mixing the metal organic framework compound, the soluble polymer and methanol, and then sequentially carrying out aerogel spraying treatment and carbonization to obtain the porous carbon spheres;
the soluble metal salt in the methanolic solution of soluble metal salt comprises a soluble zinc salt.
2. The method according to claim 1, wherein the concentration of the methanol solution of the soluble metal salt is 0.05 to 1 mol/L.
3. The method according to claim 1 or 2, wherein the soluble metal salt in the methanol solution of the soluble metal salt further comprises other soluble metal salts;
the other soluble metal salt comprises one or more of soluble cobalt salt, soluble nickel salt, soluble iron salt and soluble manganese salt.
4. The method according to claim 3, wherein when the soluble metal salt comprises a soluble zinc salt and other soluble metal salts, the molar ratio of the soluble zinc salt to the other soluble metal salts is (9-20): 1.
5. the method according to claim 1, wherein the concentration of the methanol solution of the organic ligand is 0.4 to 2 mol/L;
the organic ligand in the methanol solution of the organic ligand comprises imidazole organic matters and/or benzoic acid organic matters;
the molar ratio of the soluble metal salt in the methanol solution of the soluble metal salt to the organic ligand in the methanol solution of the organic ligand is 1 (1-6).
6. The method according to claim 1, wherein the soluble polymer comprises one or more of an ethylene oxide polymer and a polyvinyl alcohol polymer;
the concentration of the soluble polymer in the mixed solution obtained by mixing the metal organic framework compound, the soluble polymer and methanol is 0.1-2 mg/mL.
7. The method according to claim 1, wherein the temperature of the aerogel spray treatment is 300 to 800 ℃.
8. The method of claim 1, wherein the carbonizing is performed by: heating to 300 ℃ at a heating rate of 1-10 ℃/min, and then preserving heat for 1-10 h; and then heating to 900-1200 ℃ at the heating rate of 1-3 ℃/min, and preserving the heat for 3-10 h.
9. The porous carbon spheres prepared by the preparation method of any one of claims 1 to 8.
10. Use of the porous carbon spheres of claim 9 in a lithium sulfur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011550559.3A CN112661137B (en) | 2020-12-24 | 2020-12-24 | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011550559.3A CN112661137B (en) | 2020-12-24 | 2020-12-24 | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112661137A true CN112661137A (en) | 2021-04-16 |
| CN112661137B CN112661137B (en) | 2022-08-30 |
Family
ID=75409939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011550559.3A Active CN112661137B (en) | 2020-12-24 | 2020-12-24 | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661137B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675402A (en) * | 2021-07-20 | 2021-11-19 | 华南理工大学 | Metal-nitrogen doped porous carbon material and preparation method and application thereof |
| CN114751395A (en) * | 2022-05-24 | 2022-07-15 | 福州大学 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
| CN116462180A (en) * | 2023-05-06 | 2023-07-21 | 四川兴储能源科技有限公司 | Amorphous carbon, preparation method thereof, amorphous carbon cathode and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN105152281A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of capacitive type desalination electrode prepared from hierarchical porous carbon material with core-shell structure |
| CN108455562A (en) * | 2018-05-07 | 2018-08-28 | 中南大学 | A kind of thin wall type local graphitization porous carbon ball material and preparation method thereof and the application in lithium-sulfur cell |
| CN109755545A (en) * | 2019-03-07 | 2019-05-14 | 清远佳致新材料研究院有限公司 | Porous carbon materials and preparation method thereof, porous carbon/sulphur composite material, cell positive material, lithium-sulfur cell and its application |
| CN110571418A (en) * | 2019-09-05 | 2019-12-13 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
-
2020
- 2020-12-24 CN CN202011550559.3A patent/CN112661137B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN105152281A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of capacitive type desalination electrode prepared from hierarchical porous carbon material with core-shell structure |
| CN108455562A (en) * | 2018-05-07 | 2018-08-28 | 中南大学 | A kind of thin wall type local graphitization porous carbon ball material and preparation method thereof and the application in lithium-sulfur cell |
| CN109755545A (en) * | 2019-03-07 | 2019-05-14 | 清远佳致新材料研究院有限公司 | Porous carbon materials and preparation method thereof, porous carbon/sulphur composite material, cell positive material, lithium-sulfur cell and its application |
| CN110571418A (en) * | 2019-09-05 | 2019-12-13 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MIN JIANG等: "ZIF-8@Polyvinylpyrrolidone Nanocomposites Based N-Doped Porous Carbon for Highly Efficient Oxygen Reduction Reaction in Alkaline Solution", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》, vol. 163, no. 6, 31 December 2016 (2016-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675402A (en) * | 2021-07-20 | 2021-11-19 | 华南理工大学 | Metal-nitrogen doped porous carbon material and preparation method and application thereof |
| CN114751395A (en) * | 2022-05-24 | 2022-07-15 | 福州大学 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
| CN114751395B (en) * | 2022-05-24 | 2023-07-21 | 福州大学 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
| CN116462180A (en) * | 2023-05-06 | 2023-07-21 | 四川兴储能源科技有限公司 | Amorphous carbon, preparation method thereof, amorphous carbon cathode and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112661137B (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shrivastav et al. | Metal-organic frameworks (MOFs) and their composites as electrodes for lithium battery applications: Novel means for alternative energy storage | |
| CN112661137B (en) | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN106410153B (en) | A kind of titanium nitride cladding nickel titanate composite material and preparation method and application | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| CN107768636A (en) | A kind of preparation method of high power capacity fluoride/porous carbon composite anode material | |
| CN111646459A (en) | Preparation method and application of boron-doped graphene material | |
| CN113161533A (en) | MOF-derived ZnO @ C composite material and application thereof | |
| CN113264519A (en) | Modified carbon nanotube and preparation method thereof, negative electrode material, negative electrode plate and lithium ion battery | |
| CN110085854B (en) | Lithium vanadium phosphate cathode material and preparation method thereof | |
| CN115148977A (en) | Preparation method of carbon material containing single atom and application of carbon material in lithium-sulfur battery | |
| US20230411609A1 (en) | Composite positive electrode material and preparation method and application thereof | |
| CN112186166A (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN115594229B (en) | Nano high-entropy oxide material, preparation method thereof and lithium-sulfur battery positive electrode material | |
| CN114551802B (en) | Preparation method and application of carbon nano rod composite material | |
| CN115939327A (en) | Carbon cathode and preparation method thereof, and lithium ion battery | |
| CN116190649A (en) | MoO grows on mesoporous hollow carbon sphere surface in situ 2 Nanosheet composite material | |
| CN113517438B (en) | Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof | |
| CN111517297B (en) | Preparation method and application of heterostructure/graphene composite material | |
| CN111446439B (en) | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery | |
| CN112678874A (en) | N-doped FeMnO3Preparation method and application of electrode material | |
| CN111816851A (en) | Hierarchical porous LiMnxFe1-xPO4Template-free hydrothermal preparation method of/C composite microsphere cathode material | |
| CN114180620B (en) | Preparation method for preparing titanium dioxide/carbon negative electrode by taking polypyrrole as template | |
| CN114864904B (en) | Selenium-based composite material, preparation method thereof and lithium-selenium battery | |
| CN108649280A (en) | A kind of secondary ferronickel full battery of high performance alkaline and preparation method thereof | |
| CN117509733B (en) | ZnMoO3/C microsphere with intrinsic Zn defect core-shell structure and preparation method 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 |