CN109461905B - 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
- CN109461905B CN109461905B CN201811155231.4A CN201811155231A CN109461905B CN 109461905 B CN109461905 B CN 109461905B CN 201811155231 A CN201811155231 A CN 201811155231A CN 109461905 B CN109461905 B CN 109461905B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- lithium
- rubidium oxide
- positive electrode
- rubidium
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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 composite material of rubidium oxide and elemental sulfur. The positive electrode material has a strong adsorption effect on polysulfide, can effectively improve the cycle stability of the lithium-sulfur battery, can also improve the volume energy density of the lithium-sulfur battery, and achieves the purposes of slowing down the dissolution and shuttling of lithium polysulfide in ether electrolyte and further improving the cycle performance of the lithium-sulfur battery.
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
With the rapid development of the related fields of portable electronic products, electric vehicles, energy storage and the like, higher and higher requirements are put forward on the performance of the battery. Therefore, it is of great strategic importance to develop a novel lithium ion secondary battery having high performance, low cost and environmental friendliness. The theoretical specific capacity of the lithium ion battery which is commercialized at present is limited by the theoretical specific capacity of 300 mAh/g, and obviously cannot meet the requirement on the practical application quality of the lithium ion battery, and the theoretical specific capacity of the novel lithium-sulfur battery is about five times of the theoretical specific capacity of the commercial lithium ion battery (the theoretical specific capacity is 1675mAh/g, and the specific energy is 2500 Wh/kg), so that the novel lithium-sulfur battery is considered to be one of high-energy batteries with the most development potential.
However, lithium sulfur batteries still have some key problems in practical application. First, the positive electrode material has poor conductivity: the conductivity of sulfur at room temperature is 5 multiplied by 10-30S/cm, which is a typical electronic and ionic insulator; secondly, the intermediate product lithium polysulfide formed in the charging and discharging process is easily dissolved in the electrolyte solution, so that the electroactive substances on the positive electrode are pulverized, dropped and dissolved and lost, the lithium polysulfide dissolved in the electrolyte is diffused to the lithium metal negative electrode, and the lithium sulfide generated by the reaction is precipitated on the surface of the negative electrode, so that the internal resistance of the battery is increased, and finally the capacity of the battery is attenuated; third, sulfur and final product Li2The sulfur positive electrode undergoes volume expansion and fragmentation (expansion ratio of 76%) depending on the density of S, which results in poor cycle stability of the lithium-sulfur battery. The scheme for improving the performance of the lithium-sulfur battery in the prior art is to use simple substances through a filling, mixing or coating methodAnd (3) mechanically compounding sulfur and a porous material with a high pore structure to form a positive electrode composite material, so that the lithium ion conductivity of the sulfur-based positive electrode and the cycle performance of the battery are improved. The porous material needs to meet the following requirements: firstly, the catalyst has chemical stability and does not react with polysulfide and metallic lithium; secondly, insoluble in electrolyte; and thirdly, the lithium ion conductivity is higher. The lithium-sulfur batteries currently on the market have a number of disadvantages: the effective load capacity of sulfur in the positive electrode material is low, the shuttle effect of polysulfide is obvious, the volume expansion effect of the lithium-sulfur battery is obvious, the electrochemical performance of the battery is unstable, the material yield is low, and the feasibility of industrial production is poor.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery positive electrode material and a preparation method thereof aiming at the defects, the positive electrode material has stronger adsorption effect on polysulfide, can effectively improve the cycle stability of the lithium-sulfur battery, can also improve the volume energy density of the lithium-sulfur battery, and achieves the purposes of slowing down the dissolution and shuttle of lithium polysulfide in ether electrolyte and further improving the cycle performance of the lithium-sulfur battery.
The technical scheme of the invention is as follows: a positive electrode material of lithium-sulfur battery is prepared from rubidium oxide and sulfur
A composite material of simple substances.
The weight percentage of the sulfur simple substance in the composite material is 50-90%.
A preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparing rubidium oxide: firstly, mixing rubidium nitrate and deionized water, fully stirring to obtain a mixed solution,
adding NaOH into the mixed solution, uniformly stirring, placing the mixture into a reaction kettle, sealing, and carrying out reaction at the temperature of 180-200 DEG C
Preserving heat for 12-15 hours; after the reaction is finished, washing the precipitate for 3 times by using deionized water, and washing by using absolute ethyl alcohol for 3 times
Secondly, drying the obtained product in a vacuum oven at the temperature of 60-80 ℃ for 6-8 hours to obtain rubidium oxide;
(2) compounding rubidium oxide and elemental sulfur: a. preparing a carbon disulfide solution of sulfur with the concentration of 10-50 mg/mL;
b. adding the rubidium oxide obtained in the step (1) into a carbon disulfide solution, and continuously stirring until carbon disulfide is completely stirred
Volatilizing to obtain rubidium oxide/sulfur compound;
c. transferring the rubidium oxide/sulfur compound into a reaction kettle, sealing the reaction kettle under the argon atmosphere, and placing the reaction kettle in a muffle
Carrying out heat treatment in a furnace, wherein the heat treatment temperature is 150-300 ℃, and the heat treatment time is 5-10 h;
and cooling to room temperature after the treatment is finished to obtain the rubidium oxide/sulfur composite anode material.
Mixing 0.5-2 g of rubidium nitrate with 50-200 mL of deionized water in the step (1), and fully stirring
And (3) obtaining a mixed solution, and then adding 1-10 mg of NaOH into the mixed solution.
And (2) adding the rubidium oxide obtained in the step (1) into 1-50 mL of carbon disulfide solution.
The invention has the beneficial effects that: according to the invention, a rubidium oxide porous material is used as a sulfur carrier material, and single sulfur and rubidium oxide are compounded to form the anode material.
The rubidium oxide has strong polarity, has strong chemical adsorption effect on lithium polysulfide, and can slow down the dissolution and shuttle of the lithium polysulfide in ether electrolyte, thereby improving the cycle stability of the lithium-sulfur battery. Meanwhile, the density of the rubidium oxide is higher, and the integral volume energy density of the lithium-sulfur battery can be improved. The initial discharge capacity of the lithium-sulfur battery adopting the anode material is 1075mAh/g under the current of 0.2C, and the capacity is 650 after 100 cycles
mAh/g, capacity retention rate 60%.
Drawings
Fig. 1 is a first-turn charge and discharge curve of the lithium-sulfur battery cathode material prepared in example 1 at a rate of 0.1C applied to a battery.
Fig. 2 is a discharge specific capacity performance curve of the lithium-sulfur battery cathode material prepared in example 2 applied to a battery at a rate of 0.1C.
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 composite material of rubidium oxide and elemental sulfur. The weight percentage of the sulfur elementary substance in the composite material is 60%.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparing rubidium oxide: firstly, 0.5g of rubidium nitrate is mixed with 50mL of deionized water and fully stirred to obtain
Mixing the solution, adding 1mg NaOH into the mixed solution, stirring, sealing in a reaction kettle, adding
Keeping the temperature for 12 hours at 180 ℃; after the reaction is finished, the precipitate is washed for 3 times by deionized water and is cleaned by absolute ethyl alcohol
Washing for 3 times, and drying the obtained product in a vacuum oven at 60 ℃ for 6 hours to obtain rubidium oxide;
(2) compounding rubidium oxide and elemental sulfur: a. preparing a carbon disulfide solution of sulfur with the concentration of 10 mg/mL;
b. adding the rubidium oxide obtained in the step (1) into 10mL of carbon disulfide solution, and continuously stirring until the carbon disulfide solution is stirred
Completely volatilizing carbon to obtain a rubidium oxide/sulfur compound;
c. transferring the rubidium oxide/sulfur compound into a reaction kettle, sealing the reaction kettle under the argon atmosphere, and placing the reaction kettle in a muffle
Carrying out heat treatment in a furnace, wherein the heat treatment temperature is 150 ℃, and the heat treatment time is 5 h; cooling after the treatment is completed
Cooling to room temperature to obtain the rubidium oxide/sulfur composite cathode material.
The prepared rubidium oxide/sulfur compound is used as an active material, carbon powder is used as a conductive agent, polyvinylidene fluoride is used as a bonding agent, the rubidium oxide/sulfur compound, the carbon powder and the polyvinylidene fluoride are placed into a mortar according to the weight ratio of (1: 8:1: 1) to be mixed and ground uniformly, and then N-methyl pyrrolidine is dropped into the mixtureGrinding the ketone solvent to slurry, uniformly coating the slurry on an aluminum foil, then drying the aluminum foil in a constant-temperature drying oven at 60 ℃ for 12h, drying the aluminum foil to constant weight, and then pressing the aluminum foil into a sheet by using a tablet press under the pressure of 5MPa, thereby preparing the positive plate of the rubidium oxide/sulfur compound lithium-sulfur battery, wherein metal lithium is used as a counter electrode and a reference electrode, the prepared positive plate of the rubidium oxide/sulfur compound lithium-sulfur battery is used as a working electrode, and 1mol/L lithium hexafluorophosphate (LiPF) is contained6) The mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate (volume ratio 1:1: 1) is used as electrolyte, porous polypropylene is used as a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon.
It can be seen from fig. 1 that the initial discharge capacity reaches 1075mAh/g, and the coulombic efficiency is also higher and reaches 95% basically.
Example 2
The positive electrode material of the lithium-sulfur battery is a composite material of rubidium oxide and elemental sulfur. The compound
The weight percentage of the sulfur in the composite material is 65%.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparing rubidium oxide: firstly, 0.7g of rubidium nitrate is mixed with 70mL of deionized water and fully stirred to obtain
Mixing the solution, adding 2mg NaOH into the mixed solution, stirring, sealing in a reaction kettle, adding
Keeping the temperature at 185 ℃ for 14 hours; after the reaction is finished, the precipitate is washed for 3 times by deionized water and is cleaned by absolute ethyl alcohol
Washing for 3 times, and drying the obtained product in a vacuum oven at 65 ℃ for 7 hours to obtain rubidium oxide;
(2) compounding rubidium oxide and elemental sulfur: a. preparing a carbon disulfide solution of sulfur with the concentration of 15 mg/mL;
b. adding the rubidium oxide obtained in the step (1) into 15mL of carbon disulfide solution, and continuously stirring until the carbon disulfide solution is stirred
Completely volatilizing carbon to obtain a rubidium oxide/sulfur compound;
c. transferring the rubidium oxide/sulfur compound into a reaction kettle, sealing the reaction kettle under the argon atmosphere, and placing the reaction kettle in a muffle
Carrying out heat treatment in a furnace, wherein the heat treatment temperature is 160 ℃, and the heat treatment time is 8 h; after the treatment is completed
And cooling to room temperature to obtain the rubidium oxide/sulfur composite cathode material.
Taking the prepared rubidium oxide/sulfur compound as an active material, carbon powder as a conductive agent, polyvinylidene fluoride as an adhesive, putting the rubidium oxide/sulfur compound in a mortar according to the weight ratio of the rubidium oxide/sulfur compound to the carbon powder to polyvinylidene fluoride =8:1:1, mixing and grinding uniformly, then dropping a N-methyl pyrrolidone solvent, grinding to slurry, uniformly coating the slurry on an aluminum foil, then putting the aluminum foil into a constant-temperature drying box at 60 ℃ for drying for 12h, drying to constant weight, and pressing into sheets by using a tablet press under the pressure of 5MPa, thereby preparing the rubidium oxide/sulfur compound lithium-sulfur battery positive plate; the metal lithium is taken as a counter electrode and a reference electrode, the prepared rubidium oxide/sulfur compound lithium-sulfur battery positive plate is taken as a working electrode, and 1mol/L lithium hexafluorophosphate (LiPF)6) The mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate (volume ratio 1:1: 1) is used as electrolyte, porous polypropylene is used as a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon.
As can be seen from FIG. 2, the capacity after 100 cycles was 650 mAh/g, and the capacity retention rate was 60%, which fully illustrates the stable electrochemical performance of the rubidium oxide/sulfur composite electrode.
Example 3
The positive electrode material of the lithium-sulfur battery is a composite material of rubidium oxide and elemental sulfur. The compound
The weight percentage of sulfur in the composite material is 70%.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparing rubidium oxide: firstly, 0.8g of rubidium nitrate is mixed with 80mL of deionized water and fully stirred to obtain
Mixing the solution, adding 3mg NaOH into the mixed solution, stirring, sealing in a reaction kettle, adding
Keeping the temperature for 13 hours at 190 ℃; after the reaction is finished, the precipitate is washed for 3 times by deionized water and is cleaned by absolute ethyl alcohol
Washing for 3 times, and drying the obtained product in a vacuum oven at 70 ℃ for 7 hours to obtain rubidium oxide;
(2) compounding rubidium oxide and elemental sulfur: a. preparing a carbon disulfide solution of sulfur with the concentration of 20 mg/mL;
b. adding the rubidium oxide obtained in the step (1) into 25mL of carbon disulfide solution, and continuously stirring until the carbon disulfide solution is stirred
Completely volatilizing carbon to obtain a rubidium oxide/sulfur compound;
c. transferring the rubidium oxide/sulfur compound into a reaction kettle, sealing the reaction kettle under the argon atmosphere, and placing the reaction kettle in a muffle
Carrying out heat treatment in a furnace, wherein the heat treatment temperature is 170 ℃, and the heat treatment time is 7 h; after the treatment is completed
And cooling to room temperature to obtain the rubidium oxide/sulfur composite cathode material.
Taking the prepared rubidium oxide/sulfur compound as an active material, carbon powder as a conductive agent, polyvinylidene fluoride as an adhesive, putting the rubidium oxide/sulfur compound in a mortar according to the weight ratio of the rubidium oxide/sulfur compound to the carbon powder to polyvinylidene fluoride =8:1:1, mixing and grinding uniformly, then dropping a N-methyl pyrrolidone solvent, grinding to slurry, uniformly coating the slurry on an aluminum foil, then putting the aluminum foil into a constant-temperature drying box at 60 ℃ for drying for 12h, drying to constant weight, and pressing into sheets by using a tablet press under the pressure of 5MPa, thereby preparing the rubidium oxide/sulfur compound lithium-sulfur battery positive plate; the metal lithium is taken as a counter electrode and a reference electrode, the prepared rubidium oxide/sulfur compound lithium-sulfur battery positive plate is taken as a working electrode, and 1mol/L lithium hexafluorophosphate (LiPF)6) The mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate (volume ratio 1:1: 1) is used as electrolyte, porous polypropylene is used as a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon.
Claims (4)
1. The positive electrode material of the lithium-sulfur battery is characterized by being a composite material of rubidium oxide and elemental sulfur; the composite material is prepared by the following steps: (1) preparing rubidium oxide: firstly, mixing rubidium nitrate and deionized water, fully stirring to obtain a mixed solution, then adding NaOH into the mixed solution, uniformly stirring, then placing the mixed solution into a reaction kettle, sealing, and preserving heat for 12-15 hours at the temperature of 180-200 ℃; after the reaction is finished, washing the precipitate for 3 times by using deionized water, washing the precipitate for 3 times by using absolute ethyl alcohol, and drying the obtained product in a vacuum oven at the temperature of 60-80 ℃ for 6-8 hours to obtain rubidium oxide;
(2) compounding rubidium oxide and elemental sulfur: a. preparing a carbon disulfide solution of sulfur with the concentration of 10-50 mg/mL;
b. adding the rubidium oxide obtained in the step (1) into a carbon disulfide solution, and continuously stirring until carbon disulfide is completely volatilized to obtain a rubidium oxide/sulfur compound;
c. transferring the rubidium oxide/sulfur compound into a reaction kettle, sealing the reaction kettle in an argon atmosphere, and placing the reaction kettle in a muffle furnace for heat treatment, wherein the heat treatment temperature is 150-300 ℃, and the heat treatment time is 5-10 hours; and cooling to room temperature after the treatment is finished to obtain the rubidium oxide/sulfur composite anode material.
2. The lithium-sulfur battery cathode material as claimed in claim 1, wherein the weight percentage of elemental sulfur in the composite material is 50-90%.
3. The positive electrode material for the lithium-sulfur battery as defined in claim 1, wherein in the step (1), 0.5-2 g of rubidium nitrate is mixed with 50-200 mL of deionized water, the mixture is stirred sufficiently to obtain a mixed solution, and 1-10 mg of NaOH is added into the mixed solution.
4. The positive electrode material for the lithium-sulfur battery according to claim 3, wherein the rubidium oxide obtained in the step (1) is added into 1-50 mL of carbon disulfide solution in the step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155231.4A CN109461905B (en) | 2018-09-30 | 2018-09-30 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155231.4A CN109461905B (en) | 2018-09-30 | 2018-09-30 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109461905A CN109461905A (en) | 2019-03-12 |
| CN109461905B true CN109461905B (en) | 2022-01-14 |
Family
ID=65607225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811155231.4A Active CN109461905B (en) | 2018-09-30 | 2018-09-30 | Lithium-sulfur battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109461905B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2724350B2 (en) * | 1988-03-10 | 1998-03-09 | 大塚化学株式会社 | Lithium battery |
| CN102522530B (en) * | 2011-12-27 | 2014-08-20 | 雷天电池技术有限公司 | Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof |
| EP2830141B1 (en) * | 2012-03-19 | 2019-07-03 | National University Corporation Yokohama National University | Lithium-sulfur secondary cell |
| CN104300112B (en) * | 2013-07-18 | 2016-12-28 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell positive pole |
| CN108172796A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of nanometer fibrous niobium pentaoxide/sulphur composite positive pole |
-
2018
- 2018-09-30 CN CN201811155231.4A patent/CN109461905B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109461905A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109437123B (en) | Selenium-doped ferrous disulfide carbon-coated composite material and preparation method and application thereof | |
| CN108054350B (en) | Lithium-sulfur battery composite positive electrode material and preparation method thereof | |
| CN108321438B (en) | Full-graphite lithium-sulfur battery and preparation method thereof | |
| CN112018344B (en) | Carbon-coated nickel sulfide electrode material and preparation method and application thereof | |
| CN104600296A (en) | Preparation method of Se-C positive electrode composite material of lithium-selenium battery | |
| CN105047916A (en) | Method for improving electrochemical properties of lithium iron phosphate with copper/graphene | |
| CN112038591A (en) | Magnesium-sulfur battery, transition metal sulfide/sulfur composite positive electrode material and composite method | |
| CN107331856B (en) | Core-shell structure material, preparation method and application thereof | |
| CN106129375A (en) | A kind of method of compound lithium salts modified electrode material | |
| WO2017139982A1 (en) | Preparation method for boron-nitrogen codoped three-dimensionally structured lithium-sulfur battery positive electrode material | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN109004233B (en) | Preparation method and application of layered double hydroxide-loaded lithium metal negative electrode composite copper foil current collector | |
| CN108539158B (en) | rGO/WS2Preparation method of composite material and application of composite material in positive electrode material of lithium-sulfur battery | |
| JP2021534554A (en) | Sulfur-based positive electrode active material for solid-state batteries and its preparation method and application | |
| CN108091835B (en) | Lithium-sulfur battery composite positive electrode material with sulfur loaded on cobalt ferrite and preparation method thereof | |
| CN110707309B (en) | Preparation method of ZIF8 lithium-sulfur battery cathode material with 3DOM structure | |
| CN111341973B (en) | Preparation method of functional interlayer of lithium-sulfur battery | |
| CN109346646B (en) | Novel lithium-sulfur battery diaphragm material, preparation method and application | |
| WO2017139993A1 (en) | Method for preparing doped lithium sulfide composite coated with graphene/carbon and having core-shell structure | |
| CN109461905B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN110048060B (en) | Graphene oxide loaded column pentaarene lithium-sulfur battery diaphragm, preparation method and application thereof | |
| CN110518194B (en) | Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof | |
| CN110739428B (en) | Preparation method of functional diaphragm of lithium-sulfur battery | |
| CN110571500B (en) | Lithium-sulfur semi-flow battery | |
| CN109768258B (en) | In-situ synthesis method and application of sodium vanadium phosphate-carbon-graphene nanocomposite |
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 |