CN113178554A - Preparation method of lithium-sulfur positive electrode composite material - Google Patents
Preparation method of lithium-sulfur positive electrode composite material Download PDFInfo
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- 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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a lithium-sulfur anode composite material, which is a compound of a lithium-rich manganese-based nanowire with a hollow structure and sulfur, and the method comprises the steps of firstly respectively preparing PVP organic solution and a metal salt solution containing lithium acetate, nickel acetate, cobalt acetate and manganese acetate, and then slowly dripping the metal salt solution into the PVP solution and stirring to prepare a spinning precursor solution; performing electrostatic spinning on the precursor solution to obtain precursor nanofibers; then drying the precursor nanofiber and calcining the precursor nanofiber at a certain temperature for a certain time to prepare the lithium-rich manganese-based nanowire; and finally, mixing the lithium-rich manganese-based nanowire with S, and calcining for a certain time at a certain temperature to obtain a final product. The prepared anode composite material has outstanding electrochemical performance, and the prepared electrode has high quality specific capacity, high volume specific capacity and long cycle life.
Description
Technical Field
The invention discloses a preparation method of a lithium-sulfur positive electrode composite material, and belongs to the technical field of batteries.
Background
Lithium-sulfur batteries are considered to be a new secondary battery system most likely to be put into practical use after lithium ion batteries due to the characteristics of high specific energy, cheap raw materials, environmental friendliness and the like. Through the technical clearance in recent years, the quality and energy density of the lithium-sulfur battery are continuously improved, and the prepared lithium-sulfur soft package battery has already realized 600 Wh/kg. Although having high mass energy density, its low volumetric energy density (325 Wh/L) is far below the current commercial lithium ion battery (700 Wh/L) level. At present, scholars increase the S content and select high-density carbon materials to increase the volume energy density, and although the S content is improved to a certain degree, the scholars still have great space for improvement. Meanwhile, by means of methods such as improving electrode compaction density, the volume energy density of the electrode can be obviously improved, but the porosity of the electrode is reduced, so that the wettability of the electrolyte is reduced, and the low gram capacity of the material is exerted. Meanwhile, the problems of poor cycle performance and the like caused by polysulfide shuttle effect, poor sulfur elementary substance conductivity and the like greatly limit the commercial application of the lithium-sulfur battery.
Disclosure of Invention
The invention provides a preparation method of a lithium-sulfur cathode composite material aiming at the defects in the prior art, and the preparation method is designed and provided aiming at the problems of low volume energy density, poor cycle performance and the like of the conventional lithium-sulfur battery. The preparation method designs and prepares the lithium-rich manganese-based nanowire with a hollow structure, and the material has high specific surface area and good electronic conductivity. The lithium-rich manganese-based @ S composite material is prepared by taking the sulfur-rich manganese-based @ S composite material as a sulfur carrier. The prepared composite anode material has high tap density and true density, and the volumetric specific energy of the electrode is greatly improved; meanwhile, the nano lithium-rich manganese-based material has electrocatalysis characteristics in the process of charge and discharge reaction, and polysulfide reaction kinetics are improved, so that the utilization rate of sulfur is improved, shuttle effect is inhibited, the specific capacity of electrode quality is ensured, and the cycle life is prolonged; in addition, the material has a high electrochemical window (1.6-4.8V), and can exert higher gram capacity by matching with compatible electrolyte.
The preparation method comprises the following steps:
preparing a PVP organic solution by taking PVP as a solute and DMF as a solvent, wherein the mass fraction of the PVP organic solution is 6-12%;
step two, preparing a metal salt solution by taking lithium acetate, nickel acetate, cobalt acetate and manganese acetate as solutes and DMF as a solvent, wherein the mass fraction of the metal salt solution is 12-24%;
step three, stirring PVP organic solution and slowly dripping mixed salt solution into the PVP organic solution to prepare spinning precursor solution;
step four, performing electrostatic spinning by using the spinning precursor solution to prepare precursor nanofiber; the step has the effects of synthesizing the lithium-rich manganese-based nanowire, and utilizing the agglomeration and winding characteristics of the lithium-rich manganese-based nanowire, the S can be coated in a net shape, so that the granulation effect is generated, and the dissolution of polysulfide and the like is inhibited, so that the tap density and the cycle performance of the material are improved;
step five, drying and calcining the obtained precursor nanofiber to obtain the lithium-rich manganese-based nanowire; the step is to obtain the lithium-rich manganese-based nanowire with a hollow structure, improve the specific surface area of the material, provide enough sulfur-carrying space and facilitate the adsorption of S; meanwhile, the material has the electrocatalytic property, so that the gram capacity of S is improved; compared with carbon materials, the carbon material has stronger adsorption capacity on polysulfide, inhibits the shuttle effect of polysulfide and improves the cycle stability;
and step six, calcining the lithium-rich manganese-based nanowire and S under Ar atmosphere at a certain temperature for a certain time to obtain the final lithium-sulfur composite cathode material, wherein the step has the function of uniformly compounding the lithium-rich manganese base and S to obtain the final cathode composite material with stable and excellent chemical properties.
In the implementation, the mass fraction of the PVP organic solution in the first step is 6-10%, the mass fraction of the metal salt solution in the second step is 12-20%, wherein the PVP organic solution with the mass fraction of 6% and the metal salt solution with the mass fraction of 12% are used in a matched mode, the PVP organic solution with the mass fraction of 10% and the metal salt solution with the mass fraction of 20% are used in a matched mode, and the spinning precursor solution is prepared after mixing;
in the implementation, the electrostatic spinning parameters in the fourth step are as follows: the flow rate is 0.5-3 ml/h, the spinning voltage is 10-20 kV, the humidity is 10% -40%, and the technical measures aim to obtain the lithium-rich manganese-based nanofiber with appropriate shape and size by optimizing the spinning process;
in the implementation, the calcination in the fifth step is to place the precursor nanofiber in a high-temperature tube furnace, calcine the precursor nanofiber for 2-6 h at 300-500 ℃ in the air atmosphere, and then calcine the precursor nanofiber for 5-9 h at 700-900 ℃, the purpose of selecting the process parameters is to decompose PAN, the gas generated in the process is expanded, so that the lithium-rich manganese-based material forms a nano hollow structure, an enough S-carrying space is provided, a high-efficiency conductive network is formed, and meanwhile, the lithium-rich manganese-based nanowire with low cation mixed-discharge degree and high order degree is designed and synthesized by controlling the calcination temperature and time; the calcining temperature in the step six is 100-180 ℃, the time is 8-20 hours, the process parameter is selected to perform heat treatment in inert gas, the reaction of S and air is avoided, and the uniform composition of S and the lithium-rich manganese base is ensured by optimally designing the hot-melt expansion parameter; wherein, in the fifth step, the calcination is carried out for 4h at 500 ℃, and then the calcination is carried out for 8h by heating to 750 ℃ and the calcination temperature in the sixth step is 150 ℃ and the calcination time is 20 h; in the fifth step, calcination at 500 ℃ for 4h is selected, then the temperature is raised to 800 ℃ for 7h, and the calcination temperature in the sixth step is 155 ℃ and the calcination time is 12 h.
The technical scheme of the invention is designed to simultaneously improve the energy density, the volume energy density and the cycle life, which are the bottleneck of the application research of the lithium-sulfur battery, and simultaneously solve the technical problems, thereby having important significance for developing the high-performance lithium battery technology.
Compared with the prior art, the technical scheme of the invention has the characteristics and beneficial effects that:
firstly, the lithium-rich manganese-based nanofiber with a hollow structure is generated by utilizing an electrostatic spinning technology, the material has high conductivity and high specific surface area, the electronic conductivity of elemental sulfur is improved, and meanwhile, enough space is provided for uniform deposition of S;
secondly, the lithium-rich manganese-based material has high true and tap densities compared to carbon supports. Meanwhile, the agglomeration and winding characteristics of the nanofiber structure play a role in granulation. The volume energy density of the electrode is improved finally;
and finally, the lithium-rich manganese base has an electrocatalysis effect, the shuttle effect is inhibited, the sulfur utilization rate is improved, the quality energy density of the electrode is ensured, and the cycle service life is prolonged.
By the preparation method, the preparation of the positive electrode composite material with high quality specific capacity, high volume specific capacity and long cycle life can be realized.
Detailed Description
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
The method for preparing the lithium-sulfur cathode composite material comprises the following steps:
step one, dissolving 60g of PAN in 940g of DMF solvent to prepare a PAN solution with the mass fraction of 6%;
step two, adding 1.2mol of CH3COOLi·2H2O、0.5mol Mn(CH3COO)2·4H2O、0.15mol Ni(CH3COO)2·4H2O、0.15mol Co(CH3COO)2·4H2Dissolving O in a proper amount of DMF solvent to prepare a mixed salt solution with the mass fraction of 12%;
stirring the PAN solution, slowly dropwise adding a salt solution into the PAN solution, and stirring at normal temperature for 24 hours to obtain a uniform spinning precursor solution;
and step four, injecting the prepared spinning precursor liquid into a plastic needle tube, mounting a needle head, and connecting the needle tube into an electrostatic spinning device. Wrapping the receiving plate with aluminum foil, wherein the distance between the receiving plate and the needle head is 8 cm;
step five, opening the device to spin, wherein the spinning parameters are as follows: the flow rate is 0.8ml/h, the spinning voltage is 16kV, and the humidity is 30%;
collecting the fiber felt obtained on the aluminum foil, and drying at 80 ℃;
placing the product in a high-temperature tube furnace, calcining for 4h at 500 ℃ in air atmosphere, and then heating to 750 ℃ to calcine for 8 h;
and step eight, grinding and mixing the product and S powder, placing the mixture in a muffle furnace, and calcining the mixture for 20 hours at 150 ℃ in Ar atmosphere to obtain a final product.
Example 2
The method for preparing the lithium-sulfur cathode composite material comprises the following steps:
step one, dissolving 60g of PAN in 540g of DMF solvent to prepare a PAN solution with the mass fraction of 10%;
step two, adding 1.2mol of CH3COOLi·2H2O、0.5mol Mn(CH3COO)2·4H2O、0.15mol Ni(CH3COO)2·4H2O、0.15mol Co(CH3COO)2·4H2Dissolving O in a proper amount of DMF solvent to prepare a salt solution with the mass fraction of 20%;
stirring the PAN solution, slowly dropwise adding a salt solution into the PAN solution, and stirring at normal temperature for 24 hours to obtain a uniform spinning precursor solution;
and step four, injecting the prepared spinning precursor liquid into a plastic needle tube, mounting a needle head, and connecting the needle tube into an electrostatic spinning device. Wrapping the receiving plate with aluminum foil, wherein the distance between the receiving plate and the needle head is 20 cm;
step five, opening the device to spin, wherein the spinning parameters are as follows: the flow rate is 3ml/h, the spinning voltage is 15kV, and the humidity is 40%;
collecting the fiber felt obtained on the aluminum foil, and drying at 80 ℃;
placing the product in a high-temperature tube furnace, calcining for 4h at 500 ℃ in air atmosphere, and then heating to 750 ℃ to calcine for 8 h;
and step eight, grinding and mixing the product and S powder, placing the mixture in a muffle furnace, and calcining the mixture for 20 hours at 150 ℃ in Ar atmosphere to obtain a final product.
Example 3
The method for preparing the lithium-sulfur cathode composite material comprises the following steps:
step one, dissolving 60g of PAN in 940g of DMF solvent to prepare a PAN solution with the mass fraction of 6%;
step two, adding 1.2mol of CH3COOLi·2H2O、0.54mol Mn(CH3COO)2·4H2O、0.13mol Ni(CH3COO)2·4H2O、0.13mol Co(CH3COO)2·4H2Dissolving O in a proper amount of DMF solvent to prepare a salt solution with the mass fraction of 12%;
stirring the PAN solution, slowly dropwise adding a salt solution into the PAN solution, and stirring at normal temperature for 24 hours to obtain a uniform spinning precursor solution;
and step four, injecting the prepared spinning precursor liquid into a plastic needle tube, mounting a needle head, and connecting the needle tube into an electrostatic spinning device. Wrapping the receiving plate with aluminum foil, wherein the distance between the receiving plate and the needle head is 20 cm;
step five, opening the device to spin, wherein the spinning parameters are as follows: the flow rate is 3ml/h, the spinning voltage is 15kV, and the humidity is 40%;
collecting the fiber felt obtained on the aluminum foil, and drying at 80 ℃;
placing the product in a high-temperature tube furnace, calcining for 4h at 500 ℃ in air atmosphere, and then heating to 800 ℃ for calcining for 7 h;
and step eight, grinding and mixing the product and S powder, placing the mixture in a muffle furnace, and calcining the mixture for 12 hours at 155 ℃ in Ar atmosphere to obtain a final product.
The lithium-sulfur positive electrode composite material designed and synthesized by the invention has excellent electrochemical performance, and the pole piece prepared by using the positive electrode material has the mass energy density higher than 800mAh/g and the volume energy density higher than 700mAh/cm3，0.5mA/cm2The capacity retention rate is more than 80 percent after 100 cycles under the current density.
Claims (10)
1. A preparation method of a lithium-sulfur positive electrode composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
preparing a PVP organic solution by taking PVP as a solute and DMF as a solvent, wherein the mass fraction of the PVP organic solution is 6-12%;
step two, preparing a metal salt solution by taking lithium acetate, nickel acetate, cobalt acetate and manganese acetate as solutes and DMF as a solvent, wherein the mass fraction of the metal salt solution is 12-24%;
step three, stirring PVP organic solution and slowly dripping mixed salt solution into the PVP organic solution to prepare spinning precursor solution;
step four, performing electrostatic spinning by using the spinning precursor solution to prepare precursor nanofiber;
step five, drying and calcining the obtained precursor nanofiber to obtain the lithium-rich manganese-based nanowire;
and step six, calcining the lithium-rich manganese-based nanowire and S under Ar atmosphere at a certain temperature for a certain time to obtain the final lithium-sulfur composite cathode material.
2. The method for preparing a lithium sulfur positive electrode composite material according to claim 1, characterized in that: the mass fraction of the PVP organic solution in the first step is 6-10%.
3. The method for preparing a lithium sulfur positive electrode composite material according to claim 1, characterized in that: and the mass fraction of the metal salt solution in the second step is 12-20%.
4. The method for preparing a lithium sulfur positive electrode composite material according to claim 1, characterized in that: the electrostatic spinning parameters in the fourth step are as follows: the flow rate is 0.5-3 ml/h, the spinning voltage is 10-20 kV, and the humidity is 10-40%.
5. The method for preparing a lithium sulfur positive electrode composite material according to claim 1, characterized in that: and the calcination in the fifth step is to calcine the precursor nanofiber at 300-500 ℃ for 2-6 h, and then calcine the precursor nanofiber at 700-900 ℃ for 5-9 h.
6. The method for producing a lithium sulfur positive electrode composite material according to claims 1 and 5, characterized in that: and the calcination in the step five is to place the precursor nanofiber in a high-temperature tube furnace, calcine the precursor nanofiber for 4 hours at 500 ℃ in the air atmosphere, and then heat the precursor nanofiber to 750 ℃ to calcine the precursor nanofiber for 8 hours.
7. The method for producing a lithium sulfur positive electrode composite material according to claims 1 and 5, characterized in that: and step five, the calcination is to place the precursor nanofiber in a high-temperature tube furnace, calcine the precursor nanofiber for 4 hours at 500 ℃ in the air atmosphere, and then heat the precursor nanofiber to 800 ℃ for calcination for 7 hours.
8. The method for preparing a lithium sulfur positive electrode composite material according to claim 1, characterized in that: and sixthly, calcining for 8-20 hours at the temperature of 100-180 ℃.
9. The method for producing a lithium sulfur positive electrode composite material according to claims 1 and 8, characterized in that: and the calcining temperature in the sixth step is 150 ℃, and the time is 20 h.
10. The method for producing a lithium sulfur positive electrode composite material according to claims 1 and 8, characterized in that: and the calcination temperature in the sixth step is 155 ℃, and the calcination time is 12 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768250A (en) * | 2019-01-07 | 2019-05-17 | 华南理工大学 | A kind of method of electrostatic spinning prepares the method and application of lithium-sulfur battery composite cathode material |
| CN109802119A (en) * | 2019-01-24 | 2019-05-24 | 南开大学 | A kind of lithium-rich manganese-based Heterogeneous Composite positive electrode of one-dimensional spinelle stratiform and preparation method thereof |
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110571418A (en) * | 2019-09-05 | 2019-12-13 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN110723759A (en) * | 2019-09-19 | 2020-01-24 | 江苏理士电池有限公司 | Preparation method and application of lithium-rich manganese-based solid solution cathode material |
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- 2021-04-20 CN CN202110427578.5A patent/CN113178554A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768250A (en) * | 2019-01-07 | 2019-05-17 | 华南理工大学 | A kind of method of electrostatic spinning prepares the method and application of lithium-sulfur battery composite cathode material |
| CN109802119A (en) * | 2019-01-24 | 2019-05-24 | 南开大学 | A kind of lithium-rich manganese-based Heterogeneous Composite positive electrode of one-dimensional spinelle stratiform and preparation method thereof |
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110571418A (en) * | 2019-09-05 | 2019-12-13 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN110723759A (en) * | 2019-09-19 | 2020-01-24 | 江苏理士电池有限公司 | Preparation method and application of lithium-rich manganese-based solid solution cathode material |
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Application publication date: 20210727 |