CN112151787B - 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
- CN112151787B CN112151787B CN202011216146.1A CN202011216146A CN112151787B CN 112151787 B CN112151787 B CN 112151787B CN 202011216146 A CN202011216146 A CN 202011216146A CN 112151787 B CN112151787 B CN 112151787B
- Authority
- CN
- China
- Prior art keywords
- cof
- lithium
- positive electrode
- composite material
- nanospheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery positive electrode material and a preparation method thereof. The positive electrode material is a COF nanosphere composite material doped with iron single atoms. The positive electrode material has the characteristics of high conductivity, high specific surface area and the like, and can effectively promote the conversion of polysulfide in the charge-discharge process due to the uniform dispersion of metal monoatomic atoms. The preparation method is simple, effective and easy to operate.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery positive electrode material and a preparation method thereof.
Background
The current social economy develops rapidly, the consumption of non-renewable energy sources is exhausted, meanwhile, the problems of environmental pollution, threat to human body health and the like are also caused, and the method for solving the problems is to develop and utilize renewable energy sources. Until now, many renewable energy sources have been developed and are well used, however, if the use of renewable energy sources is to be popularized, high-performance energy storage devices must be used as guarantees. In recent years, continuous research on various energy storage devices has found that lithium ion batteries are dominant not only in portability and energy density, but also in cycle life, and rechargeable lithium ion batteries are dominant in operating voltage and energy density, and have been successfully applied to the field of new energy vehicles. However, due to the limitations of cost, safety, energy density, battery life and power output, the current commercial lithium ion battery still cannot meet the requirements of large-scale energy storage and the public for different models of electric vehicles. In addition, as the demand of lithium ion batteries has increased in recent years, the reserve of lithium resources is gradually consumed. There is therefore an urgent need for researchers to make efforts to improve energy storage technologies and develop alternative battery systems based on abundant resources, and lithium sulfur battery secondary batteries are considered candidates for next-generation battery systems due to high theoretical specific capacity and high energy density.
Rechargeable lithium sulfur batteries typically consist of a lithium anode, a porous separator filled with electrolyte, and a sulfur cathode. Sulfur, an active material, is abundant on earth as a positive electrode material for lithium sulfur batteries, and is superior to other electrode materials in terms of both price and environmental problems. Compared with the traditional lithium ion battery, the lithium ion battery has obvious advantages in resource utilization, capacity density (1675 mAh/g) and energy density (2600 Wh/kg), which is also the main reason why many researchers are keen to research the positive electrode material of the lithium-sulfur battery in recent years.
However, the commercial development of lithium-sulfur batteries still has several key problems that need further improvement: firstly, the poor conductivity of the active substance sulfur reduces the electrochemical utilization rate of the active substance sulfur, so that the capacity of the lithium-sulfur battery can be rapidly reduced in the high-speed charge and discharge process; second, long-chain lithium polysulfides may dissolve in the electrolyte and then diffuse through the electrolyte to the anode lithium surface, resulting in the growth of short-chain polysulfides on the lithium anode, both hindering electron transport and consuming active material, while also increasing the impedance of the electrode. The short-chain intermediate can still diffuse back to the cathode surface due to the influence of concentration gradient and react with sulfur or polysulfide through shuttle effect, so that the coulomb efficiency and the cycle stability of the sulfur cathode are reduced; third, sulfur and lithium polysulfides undergo drastic changes in volume during repeated charging and discharging, which can destroy the integrity and stability of the positive electrode, leading to pulverization and structural disintegration of the active positive electrode material.
To solve these problems, one of the most effective strategies is to confine sulfur or polysulfide within the cavity to maintain the mechanical and electrical integrity of the electrode, and many nanostructured materials have been studied as host materials, such as various mesoporous carbons, carbon nanotubes, carbon nanofibers, carbon spheres, graphene oxide, and conductive polymers, etc. However, studies have shown that insoluble polysulfides generated during discharge are shed from the carbon surface due to low binding energy between the nonpolar carbon and the polar polysulfides, resulting in rapid capacity fade.
The metal-organic framework (MOF) can also be used as a main material to store sulfur, the advantages of combination between polysulfide and an oxidized framework are utilized, even if metal single atoms are anchored by the nitrogen-doped MOF material to increase catalytic conversion of polysulfide, the MOF has poor thermal stability and more heavy metal centers, and the host density is increased, so that the energy density of the battery is reduced, and the application of the MOF is limited.
Researchers have proposed a Covalent Organic Framework (COF) with low density, small pore size and large specific surface area as a sulfur storage material, because COF materials mostly have conductivity, and the polar functional group of COF materials is beneficial to increase the bonding effect between polysulfide and COF electrode. COF materials are therefore considered ideal materials for anchoring polysulfides in lithium sulfur batteries. However, because COFs have weaker bond energies with polysulfides during the reaction, COFs show only moderate polysulfide capture efficiency and COFs have no significant effect on the polysulfide conversion effect during the electrochemical reaction.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a positive electrode material for a lithium-sulfur battery, which has characteristics such as high conductivity and high specific surface area, and can effectively promote the conversion of polysulfide during charge and discharge due to uniform dispersion of metal monoatomic atoms, and a method for preparing the same. The preparation method is simple, effective and easy to operate.
The technical scheme of the invention is as follows: a positive electrode material of a lithium-sulfur battery is a COF nanosphere composite material doped with iron monoatomic atoms.
Firstly, preparing sea urchin-shaped COF nanospheres through solvothermal treatment; then uniformly dispersing iron monoatomic atoms on the sea urchin-shaped COF nanospheres through high-temperature annealing to obtain the COF nanosphere composite material doped with the iron monoatomic atoms.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) Preparing COF nanospheres: firstly, adding toluene and n-butanol as organic solvents, then adding squaric acid, and heating and stirring in an oil bath at 110 ℃ until the squaric acid is dissolved; adding 1,3,5-tris (4-aminophenyl) benzene, introducing argon, sealing, and oil-bathing at 120 deg.C for 3 days; centrifuging and collecting precipitates, washing the precipitates alternately by adopting n-butyl alcohol and tetrahydrofuran, and drying the precipitates to obtain COF nanospheres;
(2) Preparation of iron monoatomic doped COF nanospheres: firstly, weighing the COF nanospheres obtained in the step (1), dissolving the COF nanospheres in an acetonitrile solution, and adding FeCl 3 ·6H 2 Adding an O acetonitrile solution into the COF nanosphere acetonitrile solution, stirring at room temperature until the solution is completely adsorbed, centrifuging, and drying; and then transferring the composite material to a tubular furnace, heating the composite material to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 3 hours in flowing argon, naturally cooling the composite material to room temperature, and collecting the obtained COF nanosphere composite material doped with the iron monoatomic atoms.
The toluene in the step (1) is 10mL; the n-butyl alcohol is 20mL; the amount of squaric acid is 150mg;1,3,5-tris (4-aminophenyl) benzene is 307mg.
Introducing argon for 10min in the step (1); drying in a vacuum oven at 70 ℃.
Weighing 30mg of the COF nanosphere obtained in the step (1) in the step (2), and dissolving the COF nanosphere in 10mL of acetonitrile solution; feCl 3 ·6H 2 The concentration of the O acetonitrile solution is 10mg/mL, and the dosage is 0.03mL.
Stirring for 24 hours at room temperature in the step (2); centrifuging at 10000rpm for 5min; drying in a vacuum oven at 80 ℃.
The invention has the beneficial effects that: the COF nanospheres are reasonably designed to be used as hosts for storing sulfur and effectively adsorbing and catalytically converting polysulfide, the COF nanospheres are formed by utilizing coordination polymerization among organic matters, and then iron monoatomic atoms are uniformly dispersed into the COF nanospheres through an adsorption pyrolysis strategy to form the COF nanospheres doped with the iron monoatomic atoms. The composite material has the following excellent properties:
(1) The synthesized COF nanosphere doped with the iron monoatomic atoms is a composite material with a three-dimensional structure, and has higher specific surface area, enough open positions, good stability and an ordered framework structure. Its unique sea urchin-like structure helps to provide a path for charge and ion transport.
(2) The COF nanosphere has a large number of polar functional groups, such as oxygen-containing groups (particularly hydroxyl groups) which can be used as nucleation centers, and the active substance sulfur with good dispersion is obtained through hydrogen bonds. Since polysulfides are also polar materials, the presence of a large number of polar functional groups is beneficial to promote bonding between the polysulfides and the COF composite, thereby effectively mitigating the shuttling effect of the polysulfides.
(3) The COF is a covalent organic compound with crystallinity, is composed of light elements such as C, H, N, O and the like, is simple to synthesize and low in cost, has the advantages of carbon materials and MOF materials, and greatly improves the specific mass capacity of the lithium-sulfur battery cathode material.
(4) The iron monoatomic phase is uniformly dispersed on the COF, so that the utilization efficiency of metal atoms can be improved to the maximum extent, a polar adsorption center is provided, and the high catalytic performance of the metal monoatomic phase can be realized. In the electrochemical reaction process of the lithium-sulfur battery, polysulfide can be effectively adsorbed, the reaction kinetics are reduced, and the rapid conversion process of the polysulfide is promoted. Thereby improving the electrochemical performance of the lithium-sulfur battery.
The invention adopts a simple solvothermal method and high-temperature annealing to prepare the COF nanosphere composite material doped with the iron monoatomic atom. The method has the characteristics of low cost, simple preparation process and the like.
Drawings
Fig. 1 is an SEM image of an iron monatomic doped COF nanosphere composite prepared in example 1.
Fig. 2 is a charge and discharge curve of the iron monoatomic-doped COF nanosphere composite prepared in example 1 as a positive electrode material for a lithium-sulfur battery.
Fig. 3 is a cycle performance curve of the iron monoatomic-doped COF nanosphere composite prepared in example 1 as a positive electrode material for a lithium-sulfur battery.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
The positive electrode material of the lithium-sulfur battery is a COF nanosphere composite material doped with iron single atoms.
The preparation method of the lithium-sulfur battery cathode material comprises the following steps:
(1) Preparing COF nanospheres: firstly, adding 10mL of toluene and 20mL of n-butanol into a 500mL single-neck round-bottom flask as organic solvents, then adding 150mg of squaric acid, and heating and stirring in an oil bath at 110 ℃ until the squaric acid is dissolved; adding 307mg1,3, 5-tris (4-aminophenyl) benzene, introducing argon for 10min, rapidly sealing with a rubber plug, and oil-bathing at 120 deg.C for 3 days; centrifuging and collecting precipitates, washing the precipitates for 3 times by adopting n-butyl alcohol and tetrahydrofuran alternately, and drying the precipitates in a vacuum oven at 70 ℃ to obtain COF nanospheres;
(2) Preparing the COF nanosphere doped with the iron monoatomic atom: firstly, 30mg of COF nanosphere obtained in the step (1) is weighed and dissolved in 10mL of acetonitrile solution, and 0.03mL of FeCl with the concentration of 10mg/mL is added 3 ·6H 2 Adding an O acetonitrile solution into the COF nanosphere acetonitrile solution, strongly stirring for 24h at room temperature until complete adsorption, centrifuging for 5min at 10000rpm, no washing, and drying in a vacuum oven at 80 ℃; and then transferring the composite material to a tubular furnace, heating the composite material to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 3 hours in flowing argon, naturally cooling the composite material to room temperature, and collecting the obtained COF nanosphere composite material doped with the iron monoatomic atoms.
As can be seen from fig. 1, the COF nanosphere composite material doped with iron monoatomic ions prepared in example 1 exhibits a unique sea urchin-like three-dimensional structure.
As can be seen from fig. 2, when the COF nanosphere composite material doped with iron monoatomic atoms prepared in example 1 is used as a positive electrode material in a lithium-sulfur battery, an electrochemical charge-discharge curve shows that the first discharge capacity is 1021mAh/g at a current density of 0.2C.
As can be seen from fig. 3, when the COF nanosphere composite material doped with iron monoatomic atoms prepared in example 1 is used as a positive electrode material in a lithium-sulfur battery, a cycle performance curve shows that the first discharge capacity is 1021mAh/g at a current density of 0.2C, and the specific discharge capacity is maintained at 965mAh/g after 20 cycles of cycling.
Claims (5)
1. The positive electrode material of the lithium-sulfur battery is characterized by being a COF nanosphere composite material doped with iron single atoms;
the composite material is prepared by the following steps:
(1) Preparing COF nanospheres: firstly, adding toluene and n-butanol as organic solvents, then adding squaric acid, and heating and stirring in an oil bath at 110 ℃ until the squaric acid is dissolved; adding 1,3,5-tris (4-aminophenyl) benzene, introducing argon, sealing, and performing oil bath at 120 ℃ for 3 days; centrifuging and collecting precipitates, washing the precipitates alternately by adopting n-butyl alcohol and tetrahydrofuran, and drying the precipitates to obtain COF nanospheres;
(2) Preparation of iron monoatomic doped COF nanospheres: firstly, weighing the COF nanospheres obtained in the step (1), dissolving the COF nanospheres in an acetonitrile solution, and adding FeCl 3 ·6H 2 Adding an O acetonitrile solution into the COF nanosphere acetonitrile solution, stirring at room temperature until the adsorption is complete, centrifuging, and drying; and then transferring the composite material to a tubular furnace, heating the composite material to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 3 hours in flowing argon, naturally cooling the composite material to room temperature, and collecting the obtained COF nanosphere composite material doped with the iron monoatomic atoms.
2. The positive electrode material for lithium-sulfur batteries according to claim 1, wherein the amount of toluene in step (1) is 10mL; the n-butyl alcohol is 20mL; the amount of squaric acid is 150mg;1,3,5-tris (4-aminophenyl) benzene is 307mg.
3. The positive electrode material for the lithium-sulfur battery according to claim 1, wherein argon gas is introduced for 10min in the step (1); drying in a vacuum oven at 70 ℃.
4. The positive electrode material for the lithium-sulfur battery according to claim 1, wherein in the step (2), 30mg of the COF nanospheres obtained in the step (1) are weighed and dissolved in 10mL of acetonitrile solution; feCl 3 ·6H 2 The concentration of the O acetonitrile solution is 10mg/mL, and the dosage is 0.03mL.
5. The lithium-sulfur battery cathode material according to claim 1, wherein in the step (2), the mixture is stirred at room temperature for 24 hours; centrifuging at 10000rpm for 5min; drying in a vacuum oven at 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216146.1A CN112151787B (en) | 2020-11-04 | 2020-11-04 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216146.1A CN112151787B (en) | 2020-11-04 | 2020-11-04 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112151787A CN112151787A (en) | 2020-12-29 |
| CN112151787B true CN112151787B (en) | 2022-11-11 |
Family
ID=73953874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011216146.1A Active CN112151787B (en) | 2020-11-04 | 2020-11-04 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112151787B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993204A (en) * | 2021-03-24 | 2021-06-18 | 肇庆市华师大光电产业研究院 | Preparation method of high-specific-surface-area positive electrode material of lithium-sulfur battery |
| CN113066952B (en) * | 2021-03-24 | 2022-12-23 | 肇庆市华师大光电产业研究院 | Preparation method of high-catalytic-activity positive electrode material of lithium-sulfur battery |
| CN113130881A (en) * | 2021-04-12 | 2021-07-16 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery cathode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111206440A (en) * | 2020-03-12 | 2020-05-29 | 蚌埠学院 | Preparation method of color nanospheres with uniform particle size |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248712B (en) * | 2017-07-14 | 2021-07-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal monoatomic doped nano carbon material catalytic carrier and preparation method and application thereof |
| CN108011094B (en) * | 2017-11-10 | 2020-08-04 | 上海交通大学 | Preparation method of composite positive electrode material of lithium-sulfur battery |
| CN110368931A (en) * | 2019-07-31 | 2019-10-25 | 合肥工业大学 | A kind of preparation method of the monatomic composite material of covalent organic frame material derived carbon skeleton adulteration metal |
-
2020
- 2020-11-04 CN CN202011216146.1A patent/CN112151787B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111206440A (en) * | 2020-03-12 | 2020-05-29 | 蚌埠学院 | Preparation method of color nanospheres with uniform particle size |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112151787A (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110649267B (en) | Composite metal lithium cathode, preparation method and metal lithium battery | |
| CN112151787B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN110104630B (en) | Porous carbon composite material for battery diaphragm and preparation method and application thereof | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| WO2021104055A1 (en) | Nanomaterial and preparation method therefor, electrode, and secondary battery | |
| CN107895779B (en) | High-capacity potassium ion battery negative electrode material and preparation method and application thereof | |
| CN104064735A (en) | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof | |
| CN101764256A (en) | Rechargeable aluminum battery and preparation method thereof | |
| WO2018095202A1 (en) | Composite lithium battery and preparation method therefor | |
| CN104319371A (en) | Preparation method of lithium ion battery SnS2/CNTs/PPy composite anode material | |
| CN103943838A (en) | Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material | |
| CN110311111B (en) | N-doped CNT in-situ coated Co nanoparticle composite material and preparation and application thereof | |
| CN104064755B (en) | Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application | |
| Weng et al. | In situ growth of silicon carbide interface enhances the long life and high power of the mulberry-like Si-based anode for lithium-ion batteries | |
| CN113644269B (en) | Preparation method of nitrogen-doped hard carbon material, product and application thereof | |
| Pu et al. | Fe3P electrocatalysts assisted carbon based sandwich sulfur cathode “top–bottom” strategy for high rate and high temperature lithium–sulfur batteries | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN110752359B (en) | Preparation method of sulfur-three-dimensional hollow graphene-carbon nanotube composite lithium-sulfur battery positive electrode material | |
| CN110611068B (en) | Preparation method of novel lithium-sulfur battery diaphragm material | |
| CN105161689A (en) | Preparing method and application of polypyrrole/multi-wall carbon nanotube/sulfur composite material | |
| Zhou et al. | Surface iodine modification inducing robust CEI enables ultra-stable Li-Se batteries | |
| CN105185968B (en) | A kind of preparation method of lithium ion battery molybdenum oxide/nickel carbon composite negative pole material | |
| Xiong et al. | One-pot hydrothermal synthesis of flower-shaped Zif-67@ NiCo-LDH heterostructure as anode materials for lithium-ion batteries | |
| CN113130879B (en) | Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery | |
| CN101764257A (en) | Rechargeable aluminium-sulfur battery and preparation method 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 |