CN115602805B - Nitrogen-doped hollow carbon sphere and preparation method and application thereof - Google Patents
Nitrogen-doped hollow carbon sphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN115602805B CN115602805B CN202210507846.9A CN202210507846A CN115602805B CN 115602805 B CN115602805 B CN 115602805B CN 202210507846 A CN202210507846 A CN 202210507846A CN 115602805 B CN115602805 B CN 115602805B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- hollow carbon
- stirring
- doped hollow
- prepared
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 nitrogen-doped hollow carbon sphere and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Preparing a template melamine-formaldehyde resin ball by adopting a self-assembly method; (2) Coating the prepared template by tannic acid, and adding tetraethylenepentamine and tannic acid to perform Schiff base reaction for nitrogen doping; (3) And carrying out heat treatment on the prepared precursor to obtain the nitrogen-doped hollow carbon spheres even if the organic matters are carbonized. The preparation method is simple, the operation is simple and convenient, the repeatability is good, and the product purity is high. The prepared nitrogen-doped hollow carbon sphere material has the advantages of regular structure, good stability and high capacity as a battery anode material.
Description
Technical Field
The invention belongs to the technical field of porous anode materials, and particularly relates to a nitrogen-doped hollow carbon sphere, and a preparation method and application thereof.
Background
A number of non-carbonaceous materials with different sodium storage mechanisms have been developed as negative electrodes for sodium ion batteries, including metal oxides/sulfides (e.g., tiO 2 ，SnS 2 ，MoS 2 ) And metals/alloys (e.g. Sn, niSe 2 ). In general, these materials are being intercalated with Na + Serious volume changes still occur, resulting in reduced cycling stability. In contrast, a reasonable design and convenient synthesis of non-noble metal materials have high requirements for sodium ion batteries, and carbon materials having low price and simple fabrication have been widely studied as negative electrodes for sodium ion batteries. However, the practical application of graphite with good structure in a sodium ion battery with high energy density is hindered by the defects of low theoretical specific capacity, non-ideal rate performance and the like. In addition, other carbon materials, including porous carbon, heteroatom-doped carbon, and carbon of different structures, are also used as anode materials to increase the energy and power density of rechargeable secondary batteries.
As described above, the structural design of the carbon electrode is skillfully combined with the interlayer expansion of the carbon host to accommodate more intercalated sodium ions, which is one of the most effective ways to increase the sodium storage capacity of the carbon electrode. Therefore, development of carbon-based negative electrodes for high-performance sodium ion batteries is still a very necessary research direction.
Disclosure of Invention
The invention aims to provide a nitrogen-doped hollow carbon sphere, a preparation method and application thereof, wherein the nitrogen-doped hollow carbon sphere is prepared by a coating method on the premise of being carbonized to obtain the nitrogen-doped hollow carbon sphere which is used as a negative electrode material of a sodium ion battery. The preparation method is simple to operate, good in repeatability and high in product purity, and has high energy density, good rate capability and high specific capacity when used as a negative electrode material of a sodium ion battery.
In order to achieve the above purpose, the invention provides a preparation method of a nitrogen-doped hollow carbon sphere, which comprises the following steps:
(1) Preparing a melamine-formaldehyde resin sphere template by adopting a self-assembly method;
(2) Adding tetraethylenepentamine into the prepared template to react with tannic acid to prepare a precursor;
(3) And (3) after heat treatment of the precursor, the nitrogen-doped hollow carbon sphere can be prepared.
Further, the self-assembly method specifically comprises the following steps:
(1.1) uniformly mixing formaldehyde solution with deionized water, stirring, adding melamine, and continuously stirring;
(1.2) adding acetic acid into the mixed solution prepared in the step (1.1), continuously stirring, and centrifugally collecting a sample after stirring is completed;
(1.3) washing and drying the sample in sequence to obtain the template.
Further, the volume ratio of formaldehyde solution, deionized water and acetic acid is 4-5:100-150:0.5-1, and the volume mass ratio of formaldehyde solution to melamine is 4-5 mL: 4-5 g.
Further, the stirring speed is 95-105r/min, the stirring time with deionized water in the step (1.1) is 3-7min, the stirring time after adding melamine is 50-70min, and the stirring time in the step (1.2) is 2.5-3.5h.
Further, the rotational speed of centrifugation is 7500-8500r/min, the drying temperature is 75-85 ℃, and the drying time is 10-14h.
Further, the step (2) specifically includes the following steps:
(2.1) dispersing the template in a buffer solution, adding tannic acid, stirring uniformly, and then adding tetraethylenepentamine for continuous stirring;
(2.2) centrifuging the mixed solution obtained in the step (2.1), washing and drying to obtain a precursor.
Further, the mass volume ratio of the template to the tannic acid to the tetraethylenepentamine is 0.1g to 0.3g to 0.1-0.2 mL, the stirring rotating speeds are 95-105r/min, and the stirring time is 3-7min and 3.5-4.5h respectively;
the centrifugal speed is 7500-8500r/min, the drying temperature is 75-85 ℃, and the drying time is 10-14h.
Further, the heat treatment specifically includes the following processes: heating the precursor to 750-850 ℃ in an inert gas atmosphere at a heating rate of 2-6 ℃/min, and calcining for 100-150min. Preferably, the temperature rise rate is 5 ℃/min.
The invention also provides a nitrogen-doped hollow carbon sphere, which is prepared by adopting the preparation method of the nitrogen-doped hollow carbon sphere.
The invention also provides application of the nitrogen-doped hollow carbon sphere in preparation of button cells
The invention also provides a button cell, and the negative electrode material of the button cell is prepared by the nitrogen-doped hollow carbon sphere.
In summary, the invention has the following advantages:
1. the preparation method adopts a coating method to prepare the precursor, and then carries out carbonization to obtain the nitrogen-doped hollow carbon spheres which are used as the negative electrode material of the sodium ion battery, and the obtained material has the advantages of unique structure, uniform shape, good stability, high capacity and good rate capability as the negative electrode material.
2. The preparation method provided by the invention is simple, good in repeatability, simple and easily available in raw materials, environment-friendly, and high in purity of the prepared product.
3. According to the nitrogen-doped hollow carbon sphere material prepared by taking the MF sphere as the template, as nitrogen and carbon have similar covalent radiuses, the electron structure and charge density distribution can be effectively regulated when the nitrogen is doped into the carbon-containing material, and the sodium storage capacity is improved.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a nitrogen-doped hollow carbon sphere according to example 1 of the present invention;
FIG. 2 is a graph showing the nitrogen-doped hollow carbon sphere of example 1 of the present invention at 100mA g -1 A 100-turn charge-discharge cycle graph measured at current density;
FIG. 3 is a sample of example 2 at 1A g -1 A 500-turn charge-discharge cycle graph measured at current density;
FIG. 4 shows the reduction of carbonization temperature to 100mAg in comparative example 2 -1 Graph of 100 cycles of charge-discharge cycle measured at current density.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The percentages expressed in the present invention are weight percentages unless otherwise indicated.
Example 1
The embodiment provides a preparation method of a nitrogen-doped hollow carbon sphere, which comprises the following steps:
(1) Mixing 5mL of formaldehyde solution with 150mL of deionized water at room temperature, and stirring for 5min at a rotating speed of 100 r/min; thereafter, 5g of melamine was added to the mixture and stirred at a rotation speed of 100r/min for 60min; 1mL of acetic acid is dropwise added into the mixed solution, and stirring is carried out for 3 hours at the rotating speed of 100 r/min; after stirring, centrifugally collecting a sample by a high-speed centrifuge at a rotating speed of 8000r/min, washing with deionized water and absolute ethyl alcohol, and finally drying the sample in a constant-temperature vacuum oven at 80 ℃ for 12 hours; the white powder obtained is template MF spheres, i.e. melamine-formaldehyde resin sphere templates.
(2) 0.1g of MF balls was dispersed in 100mL of buffer (ph=8), after which 0.3g of tannic acid was added to the mixture and stirred at 100r/min for 5min; dropwise adding 0.1mL of tetraethylenepentamine into the mixed solution, and stirring for 4 hours at the rotating speed of 100 r/min;
after stirring, centrifugally collecting a sample by a high-speed centrifuge at a rotating speed of 8000r/min, washing with deionized water and absolute ethyl alcohol, and finally drying the sample in a constant-temperature vacuum oven at 80 ℃ for 12 hours; the brown powder obtained is mf@npta, the precursor.
(3) In Ar 2 In the atmosphere, 0.1g of MF@NPTA powder is calcined at 800 ℃ for 2 hours at a heating rate of 5 ℃/min, and the obtained black powder is nitrogen-doped hollow carbon spheres.
The embodiment also comprises a process of preparing a negative electrode material of the button cell by using the obtained nitrogen-doped hollow carbon spheres and further assembling the button cell, wherein the process comprises the following steps:
(1) Active material (nitrogen doped hollow carbon spheres) (80 wt%) dissolved in N-methylpyrrolidone (NMP), acetylene black (10 wt%) and polyvinylidene fluoride (PVDF) (10 wt%) were added to a mortar and ground until mixed to obtain a slurry.
(2) The slurry was coated on a copper foil and transferred to a vacuum oven at 60 ℃ for 12 hours to prepare a negative electrode material.
(3) The electrolyte consisted of 1M sodium perchlorate dissolved in ethylene carbonate/diethylene carbonate (volume ratio 1:1) and was made into button cells in a glove box.
Constant current charge and discharge tests are carried out on a NEWARE battery test system, and the cut-off voltage of the sodium ion battery is 0.01V to 3.0V; cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) voltages in the range of 0.01V to 3.0V, scan rates of 0.1mV s were performed on a VersasTAT workstation -1 The method comprises the steps of carrying out a first treatment on the surface of the ESI was obtained by applying a sine wave with an amplitude of 5mV in the frequency range of 100kHz to 0.01 Hz. All tests were performed at room temperature.
From the Transmission Electron Microscope (TEM) of FIG. 1, it can be seen that the prepared nitrogen dopingThe morphology of the hollow carbon spheres; button cells were prepared from the sodium ion cell anode material nitrogen-doped hollow carbon spheres prepared in example 1, and constant current charge and discharge tests were performed on a NEWARE cell test system, with cut-off voltage of 0.01V to 3.0V and current density of 100mA g for the sodium ion cells -1 The number of cycles was 100.
The test results are shown in FIG. 2, and it can be seen from FIG. 2 that the nitrogen-doped hollow carbon spheres prepared by the method of the invention are used for preparing button cells at 100mA g -1 After 100 cycles, the specific capacity was maintained at 339mAhg -1 The initial coulombic efficiency was 51%, mainly because of electrolyte decomposition and SEI formation on the material surface, and the subsequent coulombic efficiency tended to stabilize.
Example 2
The embodiment provides a preparation method of a nitrogen-doped hollow carbon sphere, which comprises the following steps:
(1) Mixing 4mL of formaldehyde solution with 100mL of deionized water at room temperature, and stirring for 5min at a rotating speed of 100 r/min; thereafter, 4g of melamine was added to the mixture and stirred at a rotation speed of 100r/min for 60min; dropwise adding 0.5mL of acetic acid into the mixed solution, and stirring for 3h at the rotating speed of 100 r/min; after stirring, centrifugally collecting a sample by a high-speed centrifuge at a rotating speed of 8000r/min, washing with deionized water and absolute ethyl alcohol, and finally drying the sample in a constant-temperature vacuum oven at 80 ℃ for 12 hours; the white powder obtained is template MF spheres, i.e. melamine-formaldehyde resin sphere templates.
(2) 0.1g of MF balls was dispersed in 100mL of buffer (ph=8), after which 0.3g of tannic acid was added to the mixture and stirred at 100r/min for 5min; dropwise adding 0.1mL of tetraethylenepentamine into the mixed solution, and stirring for 4 hours at the rotating speed of 100 r/min; after stirring, centrifugally collecting a sample by a high-speed centrifuge at a rotating speed of 8000r/min, washing with deionized water and absolute ethyl alcohol, and finally drying the sample in a constant-temperature vacuum oven at 80 ℃ for 12 hours; the brown powder obtained is mf@npta, the precursor.
(3) In Ar 2 Calcining 0.1g MF@NPTA powder for 2 hours at 800 ℃ in an atmosphere at a heating rate of 5 ℃/min to obtainThe black powder is nitrogen doped hollow carbon spheres.
The nitrogen-doped hollow carbon spheres prepared in example 2 were fabricated into coin cells and subjected to constant current charge and discharge tests on a NEWARE cell test system. Setting the current density to be 1Ag -1 The number of cycles was 500. All tests were performed at room temperature and the test results are shown in fig. 3.
As can be seen from FIG. 3, the nitrogen-doped hollow carbon spheres prepared by the method of the invention are used for preparing button cells, which are made of 1Ag -1 After 500 cycles, the specific capacity was kept at 181mAhg -1 It can be seen that at relatively high current densities, the capacity fade is also very small and the reversibility is very good, in addition to the first-turn coulombic efficiency, which is then kept very stable.
Comparative example 1
The preparation method of the comparative example 1 is the same as that of the example 1, and only the mass ratio of tannic acid to tetraethylenepentamine is changed to be 1:2, i.e. the amount of tetraethylenepentamine added was increased, the rest of the procedure was as in example 1.
No suspension occurs during stirring, i.e. no precursor mf@npta is generated.
Comparative example 2
The preparation method of comparative example 2 was the same as in example 1, except that in step (3), the carbonization temperature was lowered, i.e., in Ar 2 Calcining 0.1g MF@NPTA powder for 2 hours at 600 ℃ at a temperature rising rate of 5 ℃/min in the atmosphere.
Active material (nitrogen doped hollow carbon spheres) (80 wt%) dissolved in N-methylpyrrolidone (NMP), acetylene black (10 wt%) and polyvinylidene fluoride (PVDF) (10 wt%) were added to a mortar and ground until mixed. The slurry was then coated on copper foil and transferred to a vacuum oven at 60 ℃ for 12h. The electrolyte consisted of 1M sodium perchlorate dissolved in ethylene carbonate/diethylene carbonate (volume ratio 1:1). And making into button cell in glove box.
Constant current charge and discharge tests are carried out on a NEWARE battery test system, and the cut-off voltage of the sodium ion battery is 0.01V to 3.0V; cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) voltages in the range of 0.01V to 3.0V, scan rate on a VersasTAT workstationAt a rate of 0.1mVs -1 The method comprises the steps of carrying out a first treatment on the surface of the ESI was obtained by applying a sine wave with an amplitude of 5mV in the frequency range of 100kHz to 0.01 Hz. All tests were performed at room temperature. The experimental test results are poor, the circulation stability is poor, and the capacity is low. The specific results are shown in FIG. 4.
As can be seen from FIG. 4, the battery prepared in comparative example 2 has poor cycle stability, low capacity, and a capacity of 100mAg -1 After 100 cycles, the specific capacity was kept at 188mAhg -1 This is because the lower carbonization temperature results in incomplete shrinkage of the material structure, lower porosity and defects, lower specific surface area and pores are detrimental to electrolyte penetration and Na + The diffusion of ions greatly reduces the capacity.
While specific embodiments of the invention have been described in detail, it should not be construed as limiting the scope of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (8)
1. The preparation method of the nitrogen-doped hollow carbon sphere is characterized by comprising the following steps of:
(1) Preparing a melamine-formaldehyde resin sphere template by adopting a self-assembly method;
(2) Adding tetraethylenepentamine into the prepared template to react with tannic acid to prepare a precursor;
(2.1) dispersing the template in a buffer solution, adding tannic acid, stirring uniformly, and then adding tetraethylenepentamine for continuous stirring; the mass volume ratio of the template to the tannic acid to the tetraethylenepentamine is 0.1g to 0.3g to 0.1-0.2 mL; the stirring time after adding tannic acid is 3-7min, and the stirring time after adding tetraethylenepentamine is 3.5-4.5h; the stirring rotating speeds are 95-105r/min;
(2.2) centrifuging the mixed solution prepared in the step (2.1), washing and drying to prepare a precursor; the rotational speed of the centrifugation is 7500-8500r/min, the drying temperature is 75-85 ℃, and the drying time is 10-14h;
(3) After heat treatment of the precursor, the nitrogen-doped hollow carbon spheres can be prepared; the heat treatment specifically comprises the following steps: heating the precursor to 750-850 ℃ in an inert gas atmosphere at a heating rate of 2-6 ℃/min, and calcining for 100-150min.
2. The method for preparing the nitrogen-doped hollow carbon sphere according to claim 1, wherein the self-assembly method specifically comprises the following steps:
(1.1) uniformly mixing formaldehyde solution with deionized water, stirring, adding melamine, and continuously stirring;
(1.2) adding acetic acid into the mixed solution prepared in the step (1.1), continuously stirring, and centrifugally collecting a sample after stirring is completed;
(1.3) washing and drying the sample in sequence to obtain the template.
3. The method for preparing the nitrogen-doped hollow carbon spheres according to claim 2, wherein the volume ratio of the formaldehyde solution to the deionized water to the acetic acid is 4-5:100-150:0.5-1, and the volume mass ratio of the formaldehyde solution to the melamine is 4-5 mL: 4-5 g.
4. The method for preparing nitrogen-doped hollow carbon spheres according to claim 2, wherein the stirring speed is 95-105r/min, the stirring time with deionized water in the step (1.1) is 3-7min, the stirring time after adding melamine is 50-70min, and the stirring time in the step (1.2) is 2.5-3.5h.
5. The method for preparing nitrogen-doped hollow carbon spheres according to claim 2, wherein the centrifugal speed is 7500-8500r/min, the drying temperature is 75-85 ℃, and the drying time is 10-14h.
6. A nitrogen-doped hollow carbon sphere prepared by the method of any one of claims 1-5.
7. Use of the nitrogen-doped hollow carbon sphere of claim 6 in the preparation of a coin cell.
8. A button cell, characterized in that the anode material of the button cell is prepared by the nitrogen-doped hollow carbon sphere of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507846.9A CN115602805B (en) | 2022-05-10 | 2022-05-10 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507846.9A CN115602805B (en) | 2022-05-10 | 2022-05-10 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115602805A CN115602805A (en) | 2023-01-13 |
| CN115602805B true CN115602805B (en) | 2023-10-10 |
Family
ID=84841820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210507846.9A Active CN115602805B (en) | 2022-05-10 | 2022-05-10 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115602805B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116281941B (en) * | 2023-02-23 | 2023-12-12 | 成都大学 | Nitrogen-doped hollow defect carbon sphere and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905495A (en) * | 2017-03-17 | 2017-06-30 | 齐鲁工业大学 | A kind of preparation method of surface modification of carbon nanotube and composite |
| CN110729480A (en) * | 2019-10-25 | 2020-01-24 | 南开大学 | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof |
| CN113659143A (en) * | 2021-08-06 | 2021-11-16 | 东莞市创明电池技术有限公司 | Preparation method of negative electrode material of sodium ion battery, negative electrode material and sodium ion battery |
-
2022
- 2022-05-10 CN CN202210507846.9A patent/CN115602805B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905495A (en) * | 2017-03-17 | 2017-06-30 | 齐鲁工业大学 | A kind of preparation method of surface modification of carbon nanotube and composite |
| CN110729480A (en) * | 2019-10-25 | 2020-01-24 | 南开大学 | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof |
| CN113659143A (en) * | 2021-08-06 | 2021-11-16 | 东莞市创明电池技术有限公司 | Preparation method of negative electrode material of sodium ion battery, negative electrode material and sodium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| "Core-shell nano-structured carbon composites based on tannic acid for lithium-ion batteries";Chenbo Liao等;《J. Mater. Chem. A》;第4卷;第17215-17224页 * |
| "Solvent-induced synthesis of nitrogen-doped hollow carbon spheres with tunable surface morphology for supercapacitors";Feng Liu等;《Applied Surface Science》;第437卷;第217-280页 * |
| "Tunable Nitrogen-Doped Carbon Nanoparticles from Tannic Acid and Urea and Their Potential for Sustainable Soots";Thomas Berthold等;《Chem Nano Mat》;第3卷(第5期);第311-318页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115602805A (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
| CN110752356B (en) | Preparation method of sodium ion battery anode material of double-metal selenide | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN108878826B (en) | Sodium manganate/graphene composite electrode material and preparation method and application thereof | |
| CN111129475A (en) | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN111477858A (en) | Si @ TiO2Preparation method of hollow core-shell composite material | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN112125289A (en) | Metal phosphide 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 | |
| CN111477857A (en) | Hollow core-shell structure FeS2Preparation method and application of @ C nanocomposite | |
| CN111777065A (en) | Graphite modified material for lithium ion battery and preparation method thereof | |
| CN115101738A (en) | Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof | |
| CN115602805B (en) | Nitrogen-doped hollow carbon sphere and preparation method and application thereof | |
| CN116281941B (en) | Nitrogen-doped hollow defect carbon sphere and preparation method and application thereof | |
| CN113422009A (en) | Lithium ion battery cathode material and preparation method and application thereof | |
| CN108565427A (en) | A kind of preparation method of carbon/lithium titanate composite material | |
| CN112499682A (en) | V-shaped groove4+Self-doping of V2O5Nanowire and preparation method and application thereof | |
| CN114249322B (en) | Nanometer flower-like VO 2 （B）/V 2 CT x Preparation method of composite material and sodium ion battery | |
| CN114639827A (en) | Preparation method of iron-based fluoride composite positive electrode material | |
| CN114628655A (en) | Plant pompon hard carbon composite negative electrode material and preparation method and application thereof | |
| CN114122371A (en) | Preparation method of porous silicon-carbon negative electrode material of lithium ion battery | |
| CN114105141A (en) | Preparation method and application of oxygen-rich functional group carbon material | |
| CN113937257A (en) | Nitrogen and fluorine co-doped titanium dioxide/carbon microsphere material, preparation method thereof and application thereof in sodium ion battery | |
| CN115842131B (en) | Nitrogen-doped hard carbon material, preparation method thereof and sodium ion battery cathode material |
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 |