CN114275775A - Lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents
Lithium-sulfur battery positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114275775A CN114275775A CN202111610489.0A CN202111610489A CN114275775A CN 114275775 A CN114275775 A CN 114275775A CN 202111610489 A CN202111610489 A CN 202111610489A CN 114275775 A CN114275775 A CN 114275775A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfur battery
- graphene
- positive electrode
- electrode material
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a lithium-sulfur battery anode material and a preparation method thereof, and the preparation method comprises the following steps: 1) placing graphene, nitrogen-containing organic matter, transition metal salt and a dispersing agent in an aqueous solution, and uniformly dispersing; 2) preparing the obtained solution into composite microspheres by a spray drying technology; 3) and (3) calcining at high temperature under the protection of inert atmosphere to obtain the catalyst-loaded graphene-carbon nanotube composite material. 4) And carrying sulfur on the material to obtain the lithium-sulfur battery cathode material. The method utilizes simple raw materials, realizes in-situ growth of the carbon nano tube on the graphene nanosheet through a spray drying method, effectively solves the shuttle effect of lithium polysulfide (LiPSs) through the prepared lithium-sulfur battery cathode material, has good cycle performance, and is simple and easy to implement and mass production.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery positive electrode material and a preparation method thereof.
Background
At present, the energy density of the traditional lithium ion battery is limited by the theoretical capacity of anode and cathode materials, and the requirement of the increasing electric automobile and the like on a high-energy-density energy storage device cannot be met. Lithium-sulfur batteries are considered to be one of the important development directions for next-generation electrochemical energy storage devices due to their very high theoretical capacity (1675mAh/g) and energy density (2600 Wh/Kg). However, the development and future commercial application of lithium sulfur batteries are still limited by many factors, such as very low conductivity of sulfur and its discharge product, lithium sulfide, performance degradation due to volume change of sulfur during charge and discharge, and shuttling effect of polysulfide as a charge and discharge intermediate.
In order to overcome the problems, in the preparation process of the sulfur positive electrode, a carbon material with high conductivity, high specific surface and rich pore structure is generally adopted as a sulfur carrier material, sulfur is uniformly dispersed on the surface of the carbon material through physical adsorption, the conductivity of the electrode is improved, and polysulfide with a pore structure and a physical limited domain is utilized. However, the acting force between the nonpolar carbon material and the polar lithium polysulfide is weak, the improvement of the cycle performance of the lithium sulfur battery is limited, and the performance of the lithium sulfur battery can be further improved by combining the measures of heteroatom doping modification, catalytic center introduction and the like.
Disclosure of Invention
The invention provides a preparation method of a lithium-sulfur battery cathode material to overcome the defects of the prior art. The preparation method comprises the steps of realizing in-situ growth of the carbon nano tube on the surface of the graphene through a simple spray drying technology and subsequent high-temperature treatment, constructing a high-efficiency conductive network, enhancing the transmission rate of electrons and ions in the lithium-sulfur battery, and simultaneously catalyzing lithium polysulfide to be rapidly converted by the metal catalytic center to inhibit a shuttle effect in the lithium-sulfur battery so as to improve the electrochemical performance of the battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a lithium-sulfur battery positive electrode material comprises the following steps:
(1) placing graphene, nitrogen-containing organic matter, transition metal salt and a dispersing agent in an aqueous solution, and uniformly dispersing to obtain a suspension;
(2) spray drying the suspension;
(3) calcining the material obtained after spray drying at high temperature in an argon atmosphere to obtain the transition metal doped graphene-carbon nanotube composite microsphere;
(4) and placing the transition metal doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank for ball milling, and then placing in a reaction kettle filled with argon for reaction to obtain the lithium-sulfur battery cathode material.
Further, the graphene is selected from one or more of single-layer graphene, double-layer graphene and few-layer graphene with 3-10 layers; the diameter distribution of the graphene is 1-50 mu m; the nitrogen-containing organic matter is selected from one or two of modified melamine, urea, biuret and polydopamine; the transition metal salt is one or more of cobalt chloride, cobalt nitrate, nickel chloride, nickel nitrate, ferric chloride and ferric nitrate; the dispersant is polyvinylpyrrolidone (PVP).
The preparation method of the modified melamine comprises the following steps:
(1) adding melamine into ethanol, and stirring for 4 hours, wherein the mass ratio of the melamine to the ethanol is 1: 10-1: 20;
(2) 10 mL of HCl (37 wt%) is added to the mixture and stirred for 2h, and the precipitate is collected by centrifugation, washed and dried at 60 ℃ for later use.
Further, the mass ratio of the graphene to the nitrogen-containing organic matter is 1:30-1:10, the mass ratio of the graphene to the transition metal salt is 20:1-10:2, and the mass ratio of the graphene to the dispersing agent is 100:1-10: 1.
Further, the solid content of the suspension is 5-50%.
Further, the temperature of spray drying in the step (2) is 60-200 ℃.
Further, the calcination temperature in the step (3) is 400-1000 ℃, and the calcination time is 4-12 h.
Further, in the step (4), the mass ratio of the transition metal doped graphene-carbon nanotube composite microspheres to the sulfur powder is 1:9-5: 5.
Further, in the step (4), the rotation speed of ball milling is 60-250r/min, and the ball milling time is 2-10 h.
Further, the temperature of the reaction in the argon-filled reaction kettle in the step (4) is 153-157 ℃, and the reaction time is 12-24 h.
The lithium-sulfur battery positive electrode material prepared by the preparation method is provided.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1. according to the invention, simple raw materials such as graphene, nitrogen-containing organic compounds, transition metal salts and dispersing agents are utilized, and the spray drying technology is combined with further high-temperature calcination treatment, so that the in-situ growth of the carbon nano tube on the surface of the graphene nanosheet is realized, a high-efficiency conductive network is formed, and the transmission rate of electrons and ions in the lithium-sulfur battery is enhanced; 2. according to the invention, the graphene and carbon nanotube conductive material with high conductivity and large specific surface area is shaped and granulated by a spray drying technology, so that the homogenization difficulty of the lithium-sulfur positive electrode can be greatly reduced, and the improvement of the overall processing performance of the lithium-sulfur positive electrode material is facilitated. 3. A transition metal catalytic center is introduced in the spray drying process, so that the lithium polysulfide can be catalyzed to be rapidly converted, the shuttle effect in the lithium sulfur battery is inhibited, and the electrochemical performance of the battery is improved. 4. Due to the reasons, the lithium-sulfur battery cathode material prepared by the lithium-sulfur battery cathode material has higher specific discharge capacity and better cycle performance, the first specific discharge capacity of 0.1C is more than 1200mAh/g, and the capacity of 0.5C is kept above 700mAh/g after 100 cycles.
Drawings
Fig. 1 is a schematic view of a cobalt-doped graphene-carbon nanotube composite microsphere according to embodiment 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the cobalt-doped graphene-carbon nanotube composite microsphere according to embodiment 1 of the present invention.
Fig. 3 is a cycle performance curve of the cobalt-doped graphene-carbon nanotube composite microsphere according to embodiment 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 3g of modified melamine, 0.29g of CoCl2And 0.016g of PVP is placed in the aqueous solution and uniformly dispersed to obtain a suspension A, the obtained suspension A is subjected to spray drying at 160 ℃, and the material obtained after spray drying is calcined at 800 ℃ for 4h under the argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 1239mAh/g, and the capacity after 0.5C 100 cycles is 703 mAh/g. Fig. 3 shows the cycle performance curve.
Example 2
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 2g of modified melamine, 0.29g of CoCl2And 0.016g of PVP is put into the aqueous solution and uniformly dispersed to obtain a suspension liquid A, and the suspension liquid A obtained is carried out at 160 DEG CAnd (3) spray drying, and calcining the material obtained after spray drying at the high temperature of 800 ℃ for 4h in the argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, and the battery obtained by assembling is subjected to charge and discharge test in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 1131mAh/g, and the capacity after 0.5C 100 cycles is 673 mAh/g.
Example 3
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 4g of modified melamine, 0.29g of CoCl2And 0.016g of PVP is placed in the aqueous solution and uniformly dispersed to obtain a suspension A, the obtained suspension A is subjected to spray drying at 160 ℃, and the material obtained after spray drying is calcined at 800 ℃ for 4h under the argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, metal lithium is used as a battery cathode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 1154mAh/g, and the capacity after 0.5C 100 cycles is 692 mAh/g.
Example 4
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 4g of urea, 0.29g of CoCl2And 0.016g of PVP is put into the aqueous solution and is uniformly dispersed to obtain a suspension liquid A, and the suspension liquid A is preparedAnd carrying out spray drying on the obtained suspension A at 160 ℃, and calcining the material obtained after spray drying at 800 ℃ for 4h in an argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, the first discharge specific capacity at 0.1C reaches 1116mAh/g, and the capacity after 0.5C 100 cycles is 698 mAh/g.
Example 5
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 4g of biuret and 0.29g of CoCl2And 0.016g of PVP is placed in the aqueous solution and uniformly dispersed to obtain a suspension A, the obtained suspension A is subjected to spray drying at 160 ℃, and the material obtained after spray drying is calcined at 800 ℃ for 4h under the argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 1194mAh/g, and the capacity after 0.5C 100-time circulation is 708 mAh/g.
Example 6
The preparation method of the lithium-sulfur battery cathode material of the embodiment is as follows:
0.2g of graphene, 4g of polydopamine, 0.29g of CoCl2And 0.016g of PVP is put into the aqueous solution and dispersed evenly,and (3) obtaining a suspension liquid A, carrying out spray drying on the obtained suspension liquid A at 160 ℃, and calcining the material obtained after spray drying at a high temperature of 800 ℃ for 4h in an argon atmosphere to obtain the Co-doped graphene-carbon nanotube composite microsphere.
Placing the obtained Co-doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6 hours at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, heating at the temperature of 155 +/-2 ℃ for 12 hours, and obtaining the lithium-sulfur battery anode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C reaches 1254mAh/g, and the capacity after 0.5C 100-time circulation is 717 mAh/g.
Comparative example 1
The preparation method of the positive electrode material for the lithium-sulfur battery of the comparative example was as follows:
placing 0.2g of graphene, 3g of modified melamine and 0.016g of PVP in an aqueous solution, uniformly dispersing to obtain a suspension A, carrying out spray drying on the obtained suspension A at 160 ℃, and calcining the material obtained after spray drying at 800 ℃ for 4 hours in an argon atmosphere to obtain the carbon-graphene composite microsphere.
And (3) placing the obtained carbon-graphene composite microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, carrying out ball milling for 6h at the rotating speed of 150r/min, placing the ball milling product in a reaction kettle filled with argon, and heating the ball milling product at the temperature of 155 +/-2 ℃ for 12h to obtain the lithium-sulfur battery cathode material.
The lithium-sulfur battery anode material is directly used as a battery anode material, the metal lithium is used as a battery cathode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 907mAh/g, and the capacity after 0.5C 100 cycles is 514 mAh/g.
Comparative example 2
The preparation method of the positive electrode material for the lithium-sulfur battery of the comparative example was as follows:
and (3) placing 0.2g of graphene and 0.016g of PVP in an aqueous solution, uniformly dispersing to obtain a suspension liquid A, and carrying out spray drying on the obtained suspension liquid A at 160 ℃ to obtain the graphene microspheres.
And (3) placing the obtained graphene microspheres and sulfur powder in a ball milling tank according to the proportion of 3:7, ball milling for 6h at the rotating speed of 150r/min, placing in a reaction kettle filled with argon, and heating for 12h at the temperature of 155 +/-2 ℃ to obtain the lithium-sulfur battery cathode material.
The lithium-sulfur battery positive electrode material is directly used as a battery positive electrode material, metal lithium is used as a battery negative electrode material, and the assembled battery is subjected to charge and discharge tests in a voltage range of 1.8-2.8V, wherein the first discharge specific capacity at 0.1C is 919mAh/g, and the capacity after 0.5C 100-time circulation is 527 mAh/g.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
(1) placing graphene, nitrogen-containing organic matter, transition metal salt and a dispersing agent in an aqueous solution, and uniformly dispersing to obtain a suspension;
(2) spray drying the suspension;
(3) calcining the material obtained after spray drying at high temperature in an argon atmosphere to obtain the transition metal doped graphene-carbon nanotube composite microsphere;
(4) and placing the transition metal doped graphene-carbon nanotube composite microspheres and sulfur powder in a ball milling tank for ball milling, and then placing in a reaction kettle filled with argon for reaction to obtain the lithium-sulfur battery anode material.
2. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the graphene is selected from one or more of single-layer graphene, double-layer graphene and few-layer graphene with 3-10 layers; the diameter distribution of the graphene is 1-50 mu m; the nitrogen-containing organic matter is selected from one or two of modified melamine, urea, biuret and polydopamine; the transition metal salt is one or more of cobalt chloride, cobalt nitrate, nickel chloride, nickel nitrate, ferric chloride and ferric nitrate; the dispersing agent is polyvinylpyrrolidone.
3. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the mass ratio of the graphene to the nitrogen-containing organic matter is 1:30-1:10, the mass ratio of the graphene to the transition metal salt is 20:1-10:2, and the mass ratio of the graphene to the dispersing agent is 100:1-10: 1.
4. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the solid content of the suspension is 5-50%.
5. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the temperature of spray drying in the step (2) is 60-200 ℃.
6. The method of manufacturing a positive electrode for a lithium-sulfur battery according to claim 1, characterized in that: the calcination temperature in the step (3) is 400-1000 ℃, and the calcination time is 4-12 h.
7. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the mass ratio of the transition metal doped graphene-carbon nanotube composite microspheres to the sulfur powder in the step (4) is 1:9-5: 5.
8. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: in the step (4), the ball milling speed is 60-250r/min, and the ball milling time is 2-10 h.
9. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein: in the step (4), the reaction temperature in the reaction kettle filled with argon is 153-157 ℃, and the reaction time is 12-24 h.
10. The positive electrode material for a lithium-sulfur battery produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111610489.0A CN114275775A (en) | 2021-12-27 | 2021-12-27 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111610489.0A CN114275775A (en) | 2021-12-27 | 2021-12-27 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114275775A true CN114275775A (en) | 2022-04-05 |
Family
ID=80875976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111610489.0A Pending CN114275775A (en) | 2021-12-27 | 2021-12-27 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114275775A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682280A (en) * | 2012-09-07 | 2014-03-26 | 中国科学院宁波材料技术与工程研究所 | Lithium-sulfur battery, positive electrode material of battery, and preparation method of material |
| WO2017120391A1 (en) * | 2016-01-08 | 2017-07-13 | The Texas A&M University System | Large energy density batteries and methods of manufacture |
| CN110021745A (en) * | 2019-04-19 | 2019-07-16 | 陕西科技大学 | A kind of nitrogen-doped graphene and the compound multistage carbon nanomaterial and its preparation method and application of carbon nanotube |
| CN110752359A (en) * | 2019-10-29 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Preparation method of sulfur-three-dimensional hollow graphene-carbon nanotube composite lithium-sulfur battery positive electrode material |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
-
2021
- 2021-12-27 CN CN202111610489.0A patent/CN114275775A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682280A (en) * | 2012-09-07 | 2014-03-26 | 中国科学院宁波材料技术与工程研究所 | Lithium-sulfur battery, positive electrode material of battery, and preparation method of material |
| WO2017120391A1 (en) * | 2016-01-08 | 2017-07-13 | The Texas A&M University System | Large energy density batteries and methods of manufacture |
| CN110021745A (en) * | 2019-04-19 | 2019-07-16 | 陕西科技大学 | A kind of nitrogen-doped graphene and the compound multistage carbon nanomaterial and its preparation method and application of carbon nanotube |
| CN110752359A (en) * | 2019-10-29 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Preparation method of sulfur-three-dimensional hollow graphene-carbon nanotube composite lithium-sulfur battery positive electrode material |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张义永: "锂硫电池原理及正极的设计与构建", 冶金工业出版社, pages: 54 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110364693B (en) | Nano three-dimensional conductive framework/MnO 2 Preparation method of composite structure material and application of composite structure material in zinc battery anode | |
| CN108390014B (en) | Preparation method of foam nickel loaded cobalt monoxide nano material with different morphologies | |
| Chen et al. | Constructing layered double hydroxide fences onto porous carbons as high-performance cathodes for lithium–sulfur batteries | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| Chu et al. | NiO nanocrystals encapsulated into a nitrogen-doped porous carbon matrix as highly stable Li-ion battery anodes | |
| CN107611382B (en) | Graphene composite carbon-limited-domain metal oxide nano-dot material and preparation method and application thereof | |
| CN108155353B (en) | Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material | |
| CN107742707B (en) | Preparation method of nano lanthanum oxide/graphene/sulfur composite material | |
| CN108539142B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN110790322B (en) | Core-shell nickel ferrite and preparation method thereof, nickel ferrite @ C material and preparation method and application thereof | |
| CN110660981B (en) | Graphene-coated bimetallic selenide material and preparation method and application thereof | |
| CN107611395B (en) | Small-size graphene lithium-sulfur battery positive electrode material, lithium-sulfur battery prepared from small-size graphene lithium-sulfur battery positive electrode material and preparation method of small-size graphene lithium-sulfur battery positive electrode material | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN110880589B (en) | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN111403712A (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| CN108091868B (en) | Multi-dimensional composite high-performance lithium ion battery cathode material and preparation method thereof | |
| CN114242983A (en) | V-shaped groove3S4@ C composite material and preparation method and application thereof | |
| Liu et al. | Carbon nanotubes-intercalated Co-NC as a robust sulfur host for lithium-sulfur batteries | |
| CN112786865A (en) | MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material | |
| CN109888236B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN109346672B (en) | Cobalt monoxide and multi-walled carbon nanotube integrated electrode and preparation method thereof | |
| CN104852042A (en) | Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material | |
| CN110790248A (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-like structure and preparation method and application thereof | |
| CN112086642B (en) | Graphitized carbon-coated high-specific-surface-area porous carbon sphere 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 |