CN109802104B - Lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents
Lithium-sulfur battery positive electrode material and preparation method thereof Download PDFInfo
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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 material is a composite material formed by a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material and pure-phase nano sulfur powder. The nitrogen-doped carbon nanofiber-carbonized covalent organic framework material is applied to the lithium-sulfur battery, the obtained positive electrode material improves the cycle performance of the lithium-sulfur battery, and the high specific surface area and the porous structure of the positive electrode material adsorb lithium polysulfide serving as an intermediate product of electrode reaction and play a role in fixing sulfur; meanwhile, the conductivity of the material is also improved.
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 lithium ion battery is considered as one of the most potential batteries in the new century because of its high voltage of single battery, high energy density, safe and reliable use, etc. The performance of the lithium ion battery depends on the reversible lithium release/insertion capacity of the battery material to a great extent, the positive electrode material is a bottleneck hindering the development of the high-capacity lithium ion battery, and the positive electrode material is also an important factor determining the safety performance of the battery. Mainstream positive electrode materials of the existing lithium ion secondary batteries include lithium cobaltate, lithium manganate, lithium iron phosphate and the like, and although the mainstream positive electrode materials have been widely applied in many fields, the mainstream positive electrode materials have advantages and disadvantages in terms of performance and price, so that the improvement of the existing positive electrode materials and the research and development work of novel positive electrode materials by electrochemical workers have never been stopped. Further research and development work on the lithium ion secondary battery anode material is mainly focused on the aspects of improving specific capacity, improving energy density, reducing wood formation, improving cycle characteristics, improving safety and the like.
As the theoretical capacity of the existing mainstream cathode material is below 200mAh/g, the aim is to be achieved by searching for more than 200mAh/g
New material of 200 mAh/g. Electroactive materials based on "switching reactions" can provide high specific capacities and high specific energies relative to the above-mentioned positive electrode materials in which intercalation and deintercalation reactions occur, among which sulfur is considered to be one of the most promising materials. The sulfur has the electrochemical capacity of multi-electron reduction reaction, and the atomic weight of the sulfur is small, so that elemental sulfur has the theoretical specific capacity of 1675mAh/g, the theoretical battery energy density of the lithium-sulfur battery can reach 2600W/kg, which is far greater than that of a commercial secondary battery used at the present stage, and the working voltage of the lithium-sulfur battery is about 2.1V, so that the application requirements of various occasions at present can be met. In addition, the sulfur resource is rich and low in price, and the sulfur source has application advantages in the development of future chemical power sources. The lithium-sulfur secondary battery has the greatest disadvantage of poor cycle stability, and researches show that lithium polysulfide generated in the battery discharging process is easily dissolved in organic electrolyte, the lithium polysulfide dissolved in the electrolyte is diffused to reach the surface of a metal lithium cathode to perform self-discharge reaction with the metal lithium cathode, the corrosion of lithium is accelerated, and the generation of disordered lithium polysulfide is partial irreversible reaction, so that the series of problems all cause low utilization rate of electrode active substances and poor cycle performance of the battery.
Disclosure of Invention
The invention aims to provide a high-specific-capacity lithium-sulfur battery positive electrode material and a preparation method thereof aiming at the defects, the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material is applied to the lithium-sulfur battery, the obtained positive electrode material improves the cycle performance of the lithium-sulfur battery, and the high specific surface area and the porous structure thereof adsorb lithium polysulfide serving as an intermediate product of electrode reaction and play a role in sulfur fixation; meanwhile, the conductivity of the material is also improved.
The technical scheme of the invention is as follows: the positive electrode material of the lithium-sulfur battery is nitrogen-doped carbon nanofiber-carbonized covalent bond
The composite material is formed by the organic framework material and pure-phase nano sulfur powder.
The mass ratio of the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material to the pure-phase nano sulfur powder is 1: 2 to 5.
A preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of covalent organic framework materials: placing 0.5-1 g of 1, 4-phenylenediamine and 0.5-1 g of 1, 3, 5-sym-triphenylformaldehyde into a reaction tube, adding 5-10 mL of 1, 4-dioxane to dissolve and mix the two uniformly, then dropwise adding 1-5 mL of acetic acid with the mass fraction of 10-40%, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally heating to room temperature, then transferring the tube into a constant-temperature oven with the temperature of 100-150 ℃ to react for 24-48 hours, stopping heating, opening the reaction tube after the system is cooled to room temperature, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at the temperature of 60 ℃ for 12-24 hours to obtain a light yellow solid;
(2) preparing a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material: taking 1-2 g of polyacrylonitrile and 1-2 g of the covalent organic framework material prepared in the step (1), placing the materials in 10-20 mL of N, N-dimethylformamide, stirring for 12-24 hours to obtain a uniform solution, and taking the uniform solution to prepare covalent organic framework material doped polyacrylonitrile nano fibers through electrostatic spinning, wherein the spinning voltage is 10-20 kv, the acceptance distance is 10-20 cm, and the air humidity is 25-50%; placing the prepared covalent organic framework material doped polyacrylonitrile nano fiber in a tubular furnace, calcining for 2-5 hours at 500-1000 ℃ in an argon atmosphere, and cooling along with the furnace to obtain a nitrogen-doped carbon nano fiber-carbonized covalent organic framework material composite material;
(3) preparing a sulfur-nitrogen doped carbon nanofiber-carbonized covalent organic framework material: and (3) mixing the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material prepared in the step (2) and pure-phase nano sulfur powder according to the mass ratio of 1: 2-5, putting the mixture into a ball milling tank, mixing and processing the mixture for 3-5 hours by using a planetary ball mill at the rotating speed of 500-800 r/min, putting the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 8-24 hours at the temperature of 100-200 ℃ to obtain the composite lithium-sulfur battery cathode material.
The invention has the beneficial effects that: the positive electrode material of the lithium-sulfur battery is formed by compounding a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material and pure-phase nano sulfur powder. The preparation method comprises the steps of preparing covalent organic framework doped polyacrylonitrile nano-fiber by an electrostatic spinning method, then carrying out high-temperature calcination treatment to obtain nitrogen-doped carbon nano-fiber-carbonized covalent organic framework, and finally compounding pure-phase nano-sulfur powder to obtain the lithium-sulfur battery anode material.
The covalent organic framework is introduced into the composite material, the covalent organic framework material is a novel crystalline porous material which has a stable structure and is combined by organic monomer covalent bonds, the covalent organic framework material has a large pi-pi conjugated system and open and regular pore channels, is favorable for electron transfer in the material, is a conductive material with excellent performance, and when the covalent organic framework material is applied to a lithium-sulfur battery, the open and regular pore channels can play a good load role on sulfur, and the excellent conductivity of the covalent organic framework material is also suitable for being used as an electrode material.
Meanwhile, polyacrylonitrile is used as a raw material when the carbon nanofiber is prepared, nitrogen-doped carbon nanofiber is naturally obtained after the polyacrylonitrile is carbonized due to the fact that the polyacrylonitrile is rich in nitrogen elements, and the electron distribution and charge density of a C-C conjugated pi bond system are changed due to the doping of electron-rich nitrogen atoms, so that a nitrogen-containing carbon layer has multiple electrons or is alkaline, the conductivity of the carbon layer is enhanced, the rapid transfer of electrons in the charge and discharge process of a battery is facilitated, and the electrochemical performance of the carbon layer is enhanced. Meanwhile, compared with a nonpolar carbon surface, nitrogen-doped carbon can greatly improve the adsorption energy to polysulfide, particularly pyridine type nitrogen can interact with lithium in polysulfide through lone electron pairs, so that the polysulfide can be fixed, and the method has important significance for improving the cycle stability of the lithium-sulfur battery.
The invention is most creative in that the nitrogen-doped carbon nanofiber and the covalent organic framework are organically combined by adopting electrostatic spinning, and the combination is not simply superposed or replaced, so that the structure of the anode material is stable, and the nitrogen-doped carbon nanofiber and the covalent organic framework are synergistic to form an excellent sulfur carrier.
According to the invention, an electrostatic spinning method is adopted when the carbon nano fiber is prepared, the electrostatic spinning fiber can effectively regulate and control the fine structure of the fiber, besides the small diameter, the electrostatic spinning fiber also has the advantages of small aperture, high porosity, good fiber uniformity and the like, the fiber dispersibility is good, and the problem of active substance agglomeration in the battery charging and discharging process is reduced to a certain extent.
Drawings
Fig. 1 is a discharge specific capacity cycling diagram of lithium sulfur batteries applied with the positive electrode materials of the lithium sulfur batteries respectively prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2 under the condition of 0.2C.
Fig. 2 is a graph showing rate performance of the positive electrode materials for lithium sulfur batteries, prepared in example 1, example 2, example 3, comparative example 1, and comparative example 2, respectively, applied to the 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 composite material formed by a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material and pure-phase nano sulfur powder.
The mass ratio of the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material to the pure-phase nano sulfur powder is 1: 3.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of covalent organic framework materials: placing 0.8g of 1, 4-phenylenediamine and 0.8g of 1, 3, 5-trimesic aldehyde into a reaction tube, adding 8mL of 1, 4-dioxane to dissolve and mix the two, slowly adding 3mL of acetic acid with the mass fraction of 30% dropwise, immediately generating yellow solid along with the dropwise addition of the acetic acid, connecting the reaction tube into a vacuum line, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally raising the temperature to room temperature, transferring the reaction tube into a constant-temperature oven at 120 ℃ for reaction for 36 hours, stopping heating, opening the reaction tube after the system is cooled to the room temperature, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at 60 ℃ for 18 hours to obtain light yellow solid;
(2) preparing a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material: taking 1.5g of polyacrylonitrile and 1.5g of the covalent organic framework material prepared in the step (1), placing the polyacrylonitrile and the covalent organic framework material in 15mL of N, N-dimethylformamide, stirring for 18 hours to obtain a uniform solution, and taking the uniform solution to prepare covalent organic framework material doped polyacrylonitrile nano-fibers through electrostatic spinning, wherein the spinning voltage is 15 kv; receiving distance is 15 cm; air humidity is 30%; then placing the prepared covalent organic framework material doped polyacrylonitrile nano fiber in a tube furnace, calcining for 3 hours at 800 ℃ in argon atmosphere, and cooling along with the furnace to obtain the nitrogen-doped carbon nano fiber-carbonized covalent organic framework material composite material;
(3) preparing a sulfur-nitrogen doped carbon nanofiber-carbonized covalent organic framework material: and (3) mixing the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material prepared in the step (2) and pure-phase nano sulfur powder according to the mass ratio of 1: and 3, putting the mixture into a ball milling tank, mixing and processing the mixture for 4 hours by using a planetary ball mill at the rotating speed of 600r/min, putting the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 12 hours at 180 ℃ to obtain the composite lithium-sulfur battery cathode material.
As can be seen from fig. 1, at a current density of 0.2C, the specific discharge capacity of the positive electrode material obtained in example 1 applied to a lithium-sulfur battery in the first cycle is 1573 mAh/g, the specific capacity of the battery continuously decreases with the continuous cycle, and there is 1497 mAh/g after 100 cycles of the cycle, which indicates that the positive electrode material has excellent electrochemical cycling performance.
As can be seen from fig. 2, the cathode material prepared in example 1 exhibited a capacity of 1354 mAh/g even at a high current density of 2C when applied to a lithium sulfur battery, and the specific discharge capacity was restored to 1541 mAh/g when the current density was decreased again to 0.2C, indicating that the cathode material had excellent rate characteristics.
Example 2
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of covalent organic framework materials: placing 0.5g of 1, 4-phenylenediamine and 0.5g of 1, 3, 5-trimesic aldehyde into a reaction tube, adding 5mL of 1, 4-dioxane to dissolve and mix the two, slowly adding 1mL of acetic acid with the mass fraction of 10% dropwise, immediately generating yellow solid along with the dropwise addition of the acetic acid, connecting the reaction tube into a vacuum line, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally raising the temperature to room temperature, then transferring the reaction tube into a constant-temperature oven at 100 ℃ for reaction for 24 hours, stopping heating, opening the reaction tube after the system is cooled to the room temperature, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at 60 ℃ for 12 hours to obtain light yellow solid;
(2) preparing a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material: taking 1g polyacrylonitrile and 1g step (1)
Placing the covalent organic framework material prepared in the step (1) in 10mL of N, N-dimethylformamide, stirring for 12 hours to obtain a uniform solution, and performing electrostatic spinning on the uniform solution to obtain covalent organic framework material doped polyacrylonitrile nano-fibers, wherein the spinning voltage is 10 kv; receiving distance is 10 cm; air humidity 25%; then placing the prepared covalent organic framework material doped polyacrylonitrile nano fiber in a tube furnace, calcining for 2 hours at 500 ℃ in argon atmosphere, and cooling along with the furnace to obtain the nitrogen-doped carbon nano fiber-carbonized covalent organic framework material composite material;
(3) preparing a sulfur-nitrogen doped carbon nanofiber-carbonized covalent organic framework material: and (3) mixing the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material prepared in the step (2) and pure-phase nano sulfur powder according to the mass ratio of 1: 2, placing the mixture into a ball milling tank, mixing and processing the mixture for 3 hours by using a planetary ball mill at the rotating speed of 500r/min, placing the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 8 hours at the temperature of 100 ℃ to obtain the composite lithium-sulfur battery cathode material.
As can be seen from fig. 1, at a current density of 0.2C, the positive electrode material obtained in this example 2 is applied to a lithium-sulfur battery, and the discharge specific capacity of the lithium-sulfur battery in the first cycle reaches 1350 mAh/g, the specific capacity of the battery continuously decreases with the continuous progress of the cycle, 1125 mAh/g still remain after 100 cycles of the cycle, and the positive electrode material has excellent electrochemical cycling performance.
As can be seen from fig. 2, the cathode material prepared in example 2 exhibited a capacity of 867 mAh/g when applied to a lithium sulfur battery even at a high current density of 2C, and the specific discharge capacity was restored to 1263 mAh/g when the current density was lowered to 0.2C again, indicating that the cathode material had excellent rate characteristics.
Example 3
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of covalent organic framework materials: placing 1g of 1, 4-phenylenediamine and 1g of 1, 3, 5-sym-triphenylformaldehyde into a reaction tube, adding 10mL of 1, 4-dioxane to dissolve and mix the two, then dropwise adding 5mL of acetic acid with the mass fraction of 40%, immediately generating yellow solid along with the dropwise addition of the acetic acid, connecting the reaction tube into a vacuum line, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally heating to room temperature, then transferring the tube into a constant-temperature oven at 150 ℃ for reaction for 48 hours, stopping heating, cooling the system to room temperature, opening the reaction tube, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at 60 ℃ for 24 hours to obtain light yellow solid;
(2) preparing a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material: taking 2g polyacrylonitrile and 2g step (1)
Placing the covalent organic framework material prepared in the step (1) into 20mL of N, N-dimethylformamide, stirring for 24 hours to obtain a uniform solution, and performing electrostatic spinning on the uniform solution to obtain covalent organic framework material doped polyacrylonitrile nano-fibers, wherein the spinning voltage is 20 kv; receiving distance is 20 cm; air humidity 50%; then placing the prepared covalent organic framework material doped polyacrylonitrile nano fiber in a tube furnace, calcining for 5 hours at 1000 ℃ in argon atmosphere, and cooling along with the furnace to obtain the nitrogen-doped carbon nano fiber-carbonized covalent organic framework material composite material;
(3) preparing a sulfur-nitrogen doped carbon nanofiber-carbonized covalent organic framework material: and (3) mixing the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material prepared in the step (2) and pure-phase nano sulfur powder according to the mass ratio of 1: and 5, placing the mixture into a ball milling tank, mixing and processing the mixture for 5 hours by using a planetary ball mill at the rotating speed of 800r/min, placing the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 24 hours at the temperature of 200 ℃ to obtain the composite lithium-sulfur battery cathode material.
As can be seen from fig. 1, at a current density of 0.2C, the positive electrode material obtained in this example 3 is applied to a lithium-sulfur battery, and the discharge specific capacity of the lithium-sulfur battery in the first cycle is up to 1467 mAh/g, and as the cycle continues, the specific capacity of the battery continuously decreases, and 1350 mAh/g still remains after 100 cycles of the cycle, which indicates that the positive electrode material has excellent electrochemical cycle performance.
As can be seen from fig. 2, the cathode material prepared in this example 3 shows a capacity of 835 mAh/g even at a high current density of 2C when applied to a lithium-sulfur battery, and the specific discharge capacity is restored to 1324 mAh/g when the current density is lowered to 0.2C again, indicating that the cathode material has excellent rate capability.
Comparative example 1
The positive electrode material of the lithium-sulfur battery is a composite material formed by a carbonized covalent organic framework material and pure-phase nano sulfur powder.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of covalent organic framework materials: placing 0.5g of 1, 4-phenylenediamine and 0.5g of 1, 3, 5-trimesic aldehyde into a reaction tube, adding 5mL of 1, 4-dioxane to dissolve and mix the two, slowly adding 1mL of acetic acid with the mass fraction of 10% dropwise, immediately generating yellow solid along with the dropwise addition of the acetic acid, connecting the reaction tube into a vacuum line, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally raising the temperature to room temperature, then transferring the reaction tube into a constant-temperature oven at 100 ℃ for reaction for 24 hours, stopping heating, opening the reaction tube after the system is cooled to the room temperature, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at 60 ℃ for 12 hours to obtain light yellow solid; then placing the prepared covalent organic framework material in a tubular furnace, calcining for 5 hours at 1000 ℃ in an argon atmosphere, and cooling along with the furnace to obtain a carbonized covalent organic framework material;
(2) preparation of sulfur-carbonized covalent organic framework materials: and (2) mixing the carbonized covalent organic framework material prepared in the step (1) and pure-phase nano sulfur powder according to the mass ratio of 1: 2, placing the mixture into a ball milling tank, mixing and processing the mixture for 3 hours by using a planetary ball mill at the rotating speed of 500r/min, placing the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 8 hours at the temperature of 100 ℃ to obtain the composite lithium-sulfur battery cathode material.
It is apparent from fig. 1 and 2 that the electrochemical performance of comparative example 1 is lower than that of the example, which is mainly because the addition of the nitrogen-doped carbon nanofibers in the example improves the overall conductivity of the positive electrode composite material of the lithium-sulfur battery, increases the transmission speed of electrons and lithium ions, and improves the effective utilization rate of active substances, and because the nitrogen-doped carbon nanofibers effectively adsorb lithium polysulfide, the loss of active substances in the charge-discharge process is reduced, so that the electrochemical performance of the example is more excellent.
Comparative example 2
The positive electrode material of the lithium-sulfur battery is a composite material formed by nitrogen-doped carbon nanofibers and pure-phase nano sulfur powder.
The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) preparing nitrogen-doped carbon nanofiber: 1g of polyacrylonitrile was put in 10mL of N, N-dimethylformamide and stirred for 12 hours to obtain a uniform solution, and the uniform solution was subjected to electrostatic spinning (spinning voltage 10 kv; acceptance distance 10 cm; air humidity 25%). Preparing polyacrylonitrile nano-fiber; then placing the polyacrylonitrile nano-fiber in a tubular furnace, calcining for 2 hours at 500 ℃ in an argon atmosphere, and cooling along with the furnace to obtain the nitrogen-doped carbon nano-fiber;
(2) preparing a sulfur-nitrogen doped carbon nanofiber material: and (2) mixing the nitrogen-doped carbon nanofiber prepared in the step (1) with pure-phase nano sulfur powder according to the mass ratio of 1: 2, placing the mixture into a ball milling tank, mixing and processing the mixture for 3 hours by using a planetary ball mill at the rotating speed of 500r/min, placing the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 8 hours at the temperature of 100 ℃ to obtain the composite lithium-sulfur battery cathode material.
It is obvious from fig. 1 and fig. 2 that the electrochemical performance of comparative example 2 is much lower than that of the examples, mainly because the addition of the carbonized covalent organic framework material in the examples improves the sulfur loading of the lithium-sulfur battery positive electrode composite material, and the higher specific surface area and the open pore structure of the composite material have obvious positive significance for the transmission of lithium ions and electrons, so that the electrochemical performance is improved.
Claims (2)
1. The positive electrode material of the lithium-sulfur battery is characterized in that the material is a composite material formed by a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material and pure-phase nano sulfur powder; the composite material is prepared by the following steps:
(1) preparation of covalent organic framework materials: placing 0.5-1 g of 1, 4-phenylenediamine and 0.5-1 g of 1, 3, 5-sym-triphenylformaldehyde into a reaction tube, adding 5-10 mL of 1, 4-dioxane to dissolve and mix the two uniformly, then dropwise adding 1-5 mL of acetic acid with the mass fraction of 10-40%, vacuumizing under the condition of liquid nitrogen freezing, removing bubbles, sealing the tube, naturally heating to room temperature, then transferring the tube into a constant-temperature oven with the temperature of 100-150 ℃ to react for 24-48 hours, stopping heating, opening the reaction tube after the system is cooled to room temperature, centrifuging, washing, performing Soxhlet extraction, and performing vacuum drying at the temperature of 60 ℃ for 12-24 hours to obtain a light yellow solid;
(2) preparing a nitrogen-doped carbon nanofiber-carbonized covalent organic framework material: taking 1-2 g of polyacrylonitrile and 1-2 g of the covalent organic framework material prepared in the step (1), placing the materials in 10-20 mL of N, N-dimethylformamide, stirring for 12-24 hours to obtain a uniform solution, and taking the uniform solution to prepare covalent organic framework material doped polyacrylonitrile nano fibers through electrostatic spinning, wherein the spinning voltage is 10-20 kv, the receiving distance is 10-20 cm, and the air humidity is 25-50%; placing the prepared covalent organic framework material doped polyacrylonitrile nano fiber in a tubular furnace, calcining for 2-5 hours at 500-1000 ℃ in an argon atmosphere, and cooling along with the furnace to obtain a nitrogen-doped carbon nano fiber-carbonized covalent organic framework material composite material;
(3) preparing a sulfur-nitrogen doped carbon nanofiber-carbonized covalent organic framework material: and (3) mixing the nitrogen-doped carbon nanofiber-carbonized covalent organic framework material prepared in the step (2) and pure-phase nano sulfur powder according to the mass ratio of 1: 2-5, putting the mixture into a ball milling tank, mixing and processing the mixture for 3-5 hours by using a planetary ball mill at the rotating speed of 500-800 r/min, putting the mixture obtained after ball milling into a tubular furnace under the protection of nitrogen, and carrying out heat treatment for 8-24 hours at the temperature of 100-200 ℃ to obtain the composite lithium-sulfur battery cathode material.
2. The positive electrode material of the lithium-sulfur battery as claimed in claim 1, wherein the mass ratio of the nitrogen-doped carbon nanofiber-carbon covalent organic framework material to the pure-phase nano sulfur powder is 1: 2 to 5.
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| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
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