CN108550818B - Lithium-sulfur battery positive electrode material and application thereof - Google Patents

Lithium-sulfur battery positive electrode material and application thereof Download PDF

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CN108550818B
CN108550818B CN201810358646.5A CN201810358646A CN108550818B CN 108550818 B CN108550818 B CN 108550818B CN 201810358646 A CN201810358646 A CN 201810358646A CN 108550818 B CN108550818 B CN 108550818B
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sulfur
lithium
positive electrode
antimony selenide
mixed solution
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CN108550818A (en
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张永光
田园
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Synergy Innovation Institute Of Gdut Heyuan
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    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 relates to a lithium-sulfur battery anode material and application thereof. The material is prepared by the following method, comprising the following steps: dissolving antimony trichloride in triethylene glycol, and stirring to obtain a cation solution; dissolving selenium powder in the first mixed solution, and stirring to obtain a selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, stirring at 180-250 ℃ in a nitrogen atmosphere, adding a cation solution, continuously stirring, and cooling to room temperature to obtain pure Sb2Se3Antimony selenide nanorods; and secondly, putting the antimony selenide nano-rods and the sulfur powder prepared in the previous step into a mortar for sulfur separation, and reacting at the temperature of 150 ℃ and 160 ℃ for 10-16h to prepare the lithium-sulfur battery cathode material. The invention has excellent electrochemical performance as the anode pole piece of the battery.

Description

Lithium-sulfur battery positive electrode material and application thereof
Technical Field
The technical scheme of the invention relates to a positive electrode material formed by compounding a metal selenide nano material and sulfur, in particular to a preparation method of a novel positive electrode material of a lithium-sulfur battery and the lithium-sulfur battery containing the novel positive electrode material.
Background
With the coming of the mobile internet era, electric vehicles, hybrid electric vehicles and energy storage devices are rapidly developed, and the use requirements of people on energy storage systems with high efficiency and economy are greatly improved. Under such a large era background, a commercial positive electrode material (e.g., LiMn) for lithium ion batteries2O4、LiCoO2、LiFePO4Etc.) are difficult to achieve a large breakthrough in a short time due to the theoretical specific capacity limitations. Because the theoretical specific capacity of elemental sulfur is already up to 1675mAh/g, and the lithium-sulfur battery has the advantages of low price, rich reserves, environmental friendliness and the like, the lithium-sulfur battery is considered to be one of high-performance battery systems with development potential. However, there are several problems that must be overcome in order to achieve widespread practical use and commercialization of lithium sulfur batteries. First, elemental sulfur and discharge product Li2S is almost non-conductive, so that electrochemical activity is easily lost, and rate performance is reduced. Secondly, due to the presence of electricityAn intermediate product lithium polysulfide can be generated in the charging and discharging processes of the battery, the solubility of the lithium polysulfide in electrolyte is higher, so that the loss of active substances of the positive electrode is caused, the capacity of the battery is rapidly attenuated, and the cycling stability is reduced; furthermore, lithium polysulfide also diffuses into the lithium negative electrode and undergoes a self-discharge reaction with metallic lithium, thereby causing a shuttle effect, resulting in corrosion of the lithium negative electrode and a decrease in coulombic efficiency. In addition, in the process of battery cyclic charge and discharge, volume expansion can occur to the sulfur positive electrode, thereby causing electrode pulverization and structure damage, and further causing battery performance reduction. These problems seriously hamper the practical use of lithium sulfur batteries. In order to solve many problems and challenges existing in lithium-sulfur batteries at present, the microstructure design and the application of different cathode materials are used to research the compounding of different conductive materials and sulfur, so as to improve the structural morphology, improve the conductivity and inhibit the dissolution and migration of lithium polysulfide in the charging and discharging processes, and thus the method becomes one of the research hotspots and important points for improving the electrochemical performance of the lithium-sulfur battery.
At present, the types of positive electrode materials have become diversified, and research reports of sulfur positive electrode composite materials at home and abroad briefly describe the preparation methods of the materials in four aspects of metal oxide/sulfur composite positive electrode materials, metal sulfide/sulfur composite positive electrode materials, polymer/sulfur composite positive electrode materials, carbon/sulfur composite positive electrode materials and the like, and lithium-sulfur battery positive electrodes and lithium-sulfur batteries respectively prepared by applying the lithium-sulfur battery positive electrode materials. The research on the metal selenide/sulfur composite anode material is very little, and CN200710040492.7 reports antimony triselenide (Sb) for a lithium ion battery2Se3) An anode film material and a preparation method thereof, the Sb2Se3The material is prepared by a reactive pulse laser deposition method, but the method has expensive equipment and complex process.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery positive electrode material and application thereof, aiming at the defects in the prior art. The material is applied to a lithium-sulfur battery through a positive electrode material formed by compounding a metal selenide nano material and sulfur, and has good performance. The preparation method is simple and novel in structure.
The invention solves the technical problem and adopts the following technical scheme:
a positive electrode material for a lithium-sulfur battery, which is prepared by a method comprising the steps of:
first, antimony selenide (Sb) is prepared2Se3) And (3) nano-rods:
dissolving antimony trichloride in triethylene glycol, and stirring to obtain a cation solution; dissolving selenium powder in the first mixed solution, and stirring to obtain a selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, and stirring for 20-40min at 180-250 ℃ in a nitrogen atmosphere; adding the cation solution, stirring for 10-30min, cooling to room temperature, and centrifuging with high speed centrifuge to obtain pure Sb2Se3The antimony selenide nanorod is 50-300 nm in length;
wherein 0.5-2mmol of antimony trichloride is added to every 5mL of triethylene glycol; the composition of the first mixed solution is monoethanolamine and N2H4·H2O, the volume ratio of the two is 4:1, and 1-2mmol of selenium powder is added into each 1.5mL of the first mixed solution; the second mixed solution consists of polyvinylpyrrolidone and triethylene glycol, wherein 0.1g of polyvinylpyrrolidone is added in each 20ml of triethylene glycol; volume ratio cationic solution: selenium precursor solution: the second mixed solution is 5: 1-2: 10-30 parts of;
the rotating speed of the high-speed centrifuge is 6000 rap/min.
Second, prepare antimony selenide/sulfur (Sb)2Se3/S) composite lithium-sulfur battery positive electrode material:
grinding the antimony selenide nano-rods and the sulfur powder prepared in the previous step in a mortar for 10-30min, and then placing the ground antimony selenide nano-rods and the sulfur powder in a ventilated kitchen for dropwise adding CS2Grinding until no elemental sulfur is separated out, putting the material into an inner container of a polytetrafluoroethylene reaction kettle under the atmosphere of argon, reacting for 10-16h at the temperature of 150-160 ℃, and finally cooling to room temperature to prepare the antimony selenide/sulfur composite material, namely the lithium-sulfur battery positive electrode material;
wherein the mass ratio is antimony selenide nanorod: and (3) 1: 2-4 of sulfur powder.
The lithium-sulfur battery positive electrode material is applied to being used as a positive electrode plate of a button cell.
The application of the positive electrode material of the lithium-sulfur battery comprises the following steps:
the preparation method comprises the steps of placing antimony selenide/sulfur composite material, conductive carbon black and polyvinylidene fluoride in a mortar according to a medium weight ratio of 8:1:1 for mixing and grinding, then dropping N-methyl pyrrolidone for continuous grinding to form bright black slurry, coating the slurry on an aluminum foil with the coating thickness of 10-30 mu m, drying the slurry in a drying oven at 60 ℃ for 12 hours, then punching the sheet into circular sheets with corresponding diameters by using a die, placing the circular sheets under a tablet press for pressure maintaining for 2min, finally placing the circular sheets in a glove box, carrying out battery assembly according to the sequence of a positive electrode shell, an electrode plate, a diaphragm, electrolyte, a metal lithium sheet, a gasket, a spring piece and a negative electrode shell, and assembling the CR2032 battery.
The above method for preparing the positive electrode material of the lithium-sulfur battery involves commercially available raw materials, and the equipment and process used are well known to those skilled in the art.
The invention has the following beneficial effects:
compared with the prior art, the method has the following prominent substantive characteristics:
in the design process of the invention, the analogy of metal oxide/sulfur composite materials and metal sulfide/sulfur composite materials in the positive electrode materials of the lithium-sulfur battery is fully considered, and the metal compound of the same main group element (O, S, Se) and the sulfur composite positive electrode material are not applied to the lithium-sulfur battery until now. The selenium precursor solution is prepared by adopting a simple and environment-friendly triethylene glycol process, and the antimony selenide nano-rod is synthesized by adopting a low-temperature heating method. Therefore, the lithium-sulfur battery positive electrode material prepared by the invention effectively inhibits the volume expansion effect in the charging and discharging processes, and the conductivity is obviously improved. Therefore, the invention meets the requirements of environmental protection and industrial production. Pure Sb prepared by the invention2Se3The nanorod is mixed with sulfur and then is applied to a lithium-sulfur battery as a positive pole piece of the battery, the first discharge specific capacity of the nanorod can reach 1169mAh/g, and the nanorod has excellent electrochemical performance.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is an X-ray diffraction pattern of the antimony selenide/sulfur nanorod cathode material prepared in example 1.
Fig. 2 is a scanning electron microscope image of the antimony selenide/sulfur nanorod cathode material prepared in example 1.
FIG. 3 is a first charge-discharge curve of the antimony selenide/sulfur nanorods prepared in example 1, example 2 and example 3 as a positive electrode material of a lithium-sulfur battery.
Detailed Description
Example 1
First, antimony selenide (Sb) is prepared2Se3) And (3) nano-rods:
dissolving antimony trichloride in triethylene glycol, and stirring for 30min to obtain a cation solution; dissolving selenium powder in the first mixed solution, and stirring for 30min to obtain a selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, and stirring for 30min at 200 ℃ under the condition of nitrogen gas; then, the cation solution is continuously stirred for 20min, then is cooled to room temperature, and is centrifuged for 10min by a high-speed centrifuge, and finally pure Sb is obtained2Se3Antimony selenide nanorods. Wherein, 1mmol of antimony trichloride is added to every 5mL of triethylene glycol; the composition of the first mixed solution is monoethanolamine and N2H4·H2O, the volume ratio of the two is 4:1, and 1.5mmol selenium powder is added into each 1.5mL of the first mixed solution; the composition of the second mixed solution is 0.1g of polyvinylpyrrolidone and 20ml of triethylene glycol, and 0.1g of polyvinylpyrrolidone is added in each 20ml of triethylene glycol; volume ratio cationic solution: selenium precursor solution: second mixed solution ═ 5: 1.5: 20; the rotating speed of the high-speed centrifuge is 6000 rap/min. Finally obtaining the antimony selenide nano rod with the length of about 200 nm.
Second, prepare antimony selenide/sulfur (Sb)2Se3/S) composite lithium-sulfur battery positive electrode material:
respectively weighing required amount of the first step according to the mass ratio of 1:2Prepared Sb2Se3And pure phase nano S powder, grinding the pure phase nano S powder and the pure phase nano S powder in a mortar for 30min, then placing the ground powder and the pure phase nano S powder in a ventilated kitchen, and mixing sulfur (namely dropwise adding CS dropwise)2To uniformly ground Sb2Se3And S powder, then grinding, repeating the "drop-grinding" 6 times until CS2And after complete volatilization, no yellow elemental S powder is precipitated in the residual solid powder. Finally, 1mL of CS is added dropwise to every 200mg of S powder2) And then moving the sample into a glove box, putting the glove box into a reaction kettle, carrying out heat treatment at 155 ℃ for 12 hours, cooling the sample along with the furnace, putting the cooled sample into a drying oven at 80 ℃, and keeping the temperature for 24 hours to obtain the antimony selenide/sulfur composite material.
As shown in figure 1, the antimony selenide/sulfur composite material has an obvious sulfur peak and good crystallization quality.
As shown in figure 2, the rod-shaped antimony selenide material is uniformly wrapped by sulfur, so that a good sulfur mixing effect is achieved.
Step three, preparing a working electrode and assembling a battery:
antimony selenide/sulfur composite material is used as an active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a bonding agent, the materials are placed in a mortar according to a weight ratio of 8:1:1 for mixing and grinding uniformly, then a proper amount of N-methyl pyrrolidone is dropwise added until the materials are just completely dissolved, the materials are continuously ground for 0.5h to form bright black slurry with certain viscosity, a scraper is used for adjusting the scraping thickness to be 15 mu m, the slurry is uniformly scraped and coated on an aluminum foil, the aluminum foil is placed in a 60 ℃ drying box for drying for 12h, the pole piece is punched into a round pole piece with a corresponding diameter by a mould, the round pole piece is placed under a tablet press for keeping 10MPa and pressure for 2min to obtain the required positive pole piece, and finally the required positive pole piece is placed in a glove box, according to the conditions that the solvent of the positive pole shell, the positive pole piece, a diaphragm and electrolyte (the mixed solution is, the volume ratio is 1: 1; the solute is LiTFSI, wherein the concentration of the solute is 1mol/L), the metal lithium sheet, the gasket, the spring sheet and the negative electrode shell are assembled in sequence, and after the assembly is finished, the assembly is compacted and sealed by a tablet press to obtain the button CR2032 half cell. The test was carried out by a CT-ZWJ-4S-T type multichannel battery tester manufactured by Shenzhen NEWARE corporation under room temperature conditions.
As shown in FIG. 3, the first discharge specific capacity of the lithium-sulfur battery using the antimony selenide/sulfur (mass ratio 1:2) nanorod as the positive electrode material reaches 1169mAh/g (CT-ZWJ-4S-T type multi-channel battery tester manufactured by Shenzhen NEWARE company, and the test is carried out at room temperature). Because the VI main group element (O, S, Se) in the periodic table of elements can generate multi-electron electrochemical reaction with Li, the potential difference formed between the VI main group element and Li is larger, and the quantity of substances required by single charge transfer is small, the maximization of energy storage can be realized, and the lithium battery system with high theoretical energy density is provided.
Example 2
First, antimony selenide (Sb) is prepared2Se3) And (3) nano-rods:
dissolving antimony trichloride in triethylene glycol, and stirring for 30min to obtain a cation solution; dissolving selenium powder in the first mixed solution, and stirring for 30min to obtain a selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, and stirring for 30min at 200 ℃ under the condition of nitrogen gas; then, the cation solution is continuously stirred for 20min, then is cooled to room temperature, and is centrifuged for 10min by a high-speed centrifuge, and finally pure Sb is obtained2Se3Antimony selenide nanorods. Wherein, 1mmol of antimony trichloride is added to every 5mL of triethylene glycol; the composition of the first mixed solution is monoethanolamine and N2H4·H2O, the volume ratio of the two is 4:1, and 1.5mmol selenium powder is added into each 1.5mL of the first mixed solution; the composition of the second mixed solution is 0.1g of polyvinylpyrrolidone and 20ml of triethylene glycol, and 0.1g of polyvinylpyrrolidone is added in each 20ml of triethylene glycol; volume ratio cationic solution: selenium precursor solution: second mixed solution ═ 5: 1.5: 20; the rotating speed of the high-speed centrifuge is 6000 rap/min. Finally obtaining the antimony selenide nano rod with the length of about 200nm
Second, prepare antimony selenide/sulfur (Sb)2Se3/S) composite lithium-sulfur battery positive electrode material:
respectively weighing required amounts of the antimony selenide prepared in the first step and pure-phase nano sulfur powder according to the mass ratio of 1:3, putting the antimony selenide and the pure-phase nano sulfur powder into a mortar for grinding for 30min, and then putting the two into the mortarIn a ventilated kitchen, CS is dropwise added2To uniformly ground Sb2Se3And S powder, adding dropwise while grinding, repeating for several times until CS2And after complete volatilization, no yellow elemental S powder is precipitated in the residual solid powder. And then moving the sample into a glove box, putting the glove box into a reaction kettle, carrying out heat treatment at 155 ℃ for 12 hours, cooling the sample along with the furnace, putting the cooled sample into a drying oven at 80 ℃, and keeping the temperature for 24 hours to obtain the antimony selenide/sulfur composite material.
Step three, preparing a working electrode and assembling a battery:
antimony selenide/sulfur composite material is used as an active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a bonding agent, the materials are placed in a mortar according to a weight ratio of 8:1:1 for mixing and grinding uniformly, then a proper amount of N-methyl pyrrolidone is dropwise added until the materials are just completely dissolved, the materials are continuously ground for 0.5h to form bright black slurry with certain viscosity, a scraper is used for adjusting the scraping thickness to be 15 mu m, the slurry is uniformly scraped and coated on an aluminum foil, the aluminum foil is placed in a 60 ℃ drying box for drying for 12h, the pole pieces are punched into round pole pieces with corresponding diameters by a mould, the round pole pieces are placed under a tablet press for keeping 10MPa and pressure for 2min to obtain the required positive pole pieces, and finally the required positive pole pieces are placed in a glove box, and according to the conditions that the solvent of the mixed solution is formed by mixing DMC and DOL, the volume ratio is 1: 1; the solute is LiTFSI, wherein the concentration of the solute is 1mol/L), the metal lithium sheet, the gasket, the spring sheet and the negative electrode shell are assembled in sequence, and after the assembly is finished, the assembly is compacted and sealed by a tablet press to obtain the button CR2032 half cell. The test was carried out by a CT-ZWJ-4S-T type multichannel battery tester manufactured by Shenzhen NEWARE corporation under room temperature conditions.
As shown in FIG. 3, the first discharge specific capacity of the lithium-sulfur battery using the antimony selenide/sulfur (mass ratio 1:3) nanorod as the positive electrode material reaches 1091 mAh/g.
Example 3
First, antimony selenide (Sb) is prepared2Se3) And (3) nano-rods:
dissolving antimony trichloride in triethylene glycol, and stirring for 30min to obtain a cation solution; dissolving selenium powder in the first mixed solutionStirring for 30min to obtain selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, and stirring for 30min at 200 ℃ under the condition of nitrogen gas; then, the cation solution is continuously stirred for 20min, then is cooled to room temperature, and is centrifuged for 10min by a high-speed centrifuge, and finally pure Sb is obtained2Se3Antimony selenide nanorods. Wherein, 1mmol of antimony trichloride is added to every 5mL of triethylene glycol; the composition of the first mixed solution is monoethanolamine and N2H4·H2O, the volume ratio of the two is 4:1, and 1.5mmol selenium powder is added into each 1.5mL of the first mixed solution; the composition of the second mixed solution is 0.1g of polyvinylpyrrolidone and 20ml of triethylene glycol, and 0.1g of polyvinylpyrrolidone is added in each 20ml of triethylene glycol; volume ratio cationic solution: selenium precursor solution: second mixed solution ═ 5: 1.5: 20; the rotating speed of the high-speed centrifuge is 6000 rap/min. Finally obtaining the antimony selenide nano rod with the length of about 200nm
Second, prepare antimony selenide/sulfur (Sb)2Se3/S) composite lithium-sulfur battery positive electrode material:
respectively weighing required amounts of the antimony selenide prepared in the first step and pure-phase nano sulfur powder according to the mass ratio of 1:4, putting the antimony selenide and the pure-phase nano sulfur powder into a mortar for grinding for 30min, then putting the mortar into a ventilated kitchen, and dropwise adding CS (sulfur hexafluoride) dropwise2To uniformly ground Sb2Se3And S powder, adding dropwise while grinding, repeating for several times until CS2And after complete volatilization, no yellow elemental S powder is precipitated in the residual solid powder. And then moving the sample into a glove box, putting the glove box into a reaction kettle, carrying out heat treatment at 155 ℃ for 12 hours, cooling the sample along with the furnace, putting the cooled sample into a drying oven at 80 ℃, and keeping the temperature for 24 hours to obtain the antimony selenide/sulfur composite material.
Step three, preparing a working electrode and assembling a battery:
antimony selenide/sulfur composite material is used as an active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a bonding agent, the materials are placed in a mortar according to a weight ratio of 8:1:1 for mixing and grinding uniformly, then a proper amount of N-methyl pyrrolidone is dropwise added until the materials are just completely dissolved, the materials are continuously ground for 0.5h to form bright black slurry with certain viscosity, a scraper is used for adjusting the scraping thickness to be 15 mu m, the slurry is uniformly scraped and coated on an aluminum foil, the aluminum foil is placed in a 60 ℃ drying box for drying for 12h, the pole pieces are punched into round pole pieces with corresponding diameters by a mould, the round pole pieces are placed under a tablet press for keeping 10MPa and pressure for 2min to obtain the required positive pole pieces, and finally the required positive pole pieces are placed in a glove box, and according to the conditions that the solvent of the mixed solution is formed by mixing DMC and DOL, the volume ratio is 1: 1; the solute is LiTFSI, wherein the concentration of the solute is 1mol/L), the metal lithium sheet, the gasket, the spring sheet and the negative electrode shell are assembled in sequence, and after the assembly is finished, the assembly is compacted and sealed by a tablet press to obtain the button CR2032 half cell. The test was carried out by a CT-ZWJ-4S-T type multichannel battery tester manufactured by Shenzhen NEWARE corporation under room temperature conditions.
As shown in FIG. 3, the first discharge specific capacity of the lithium-sulfur battery using the antimony selenide/sulfur (mass ratio 1:4) nanorod as the cathode material reaches 1070 mAh/g.
Sb prepared by the invention2Se3The one-dimensional nanorod material can effectively increase the contact surface of an active material and electrolyte to improve the utilization rate of the active material, and the one-dimensional nanorod is favorable for forming a conductive network to improve the electronic conductivity of the electrode. In addition, the one-dimensional nanorod has good mechanical strength, and is beneficial to buffering the volume effect of active substances in the charging and discharging processes. These characteristics can help to improve the electrochemical performance of the one-dimensional nano rod applied in the battery. By different Sb2Se3In the example of the proportion of the sulfur powder, the cathode material has poor conductivity due to excessive sulfur powder, and the capacity decays rapidly, as shown in fig. 3, it can be seen that the electrochemical performance of the lithium-sulfur battery using antimony selenide/sulfur (mass ratio 1:2) as the cathode material is better.
The invention is not the best known technology.

Claims (3)

1. A positive electrode material for a lithium-sulfur battery, characterized in that the material is prepared by a method comprising the steps of:
first, antimony selenide (Sb) is prepared2Se3) And (3) nano-rods:
will trichlorinateDissolving antimony in triethylene glycol, and stirring to obtain a cation solution; dissolving selenium powder in the first mixed solution, and stirring to obtain a selenium precursor solution; pouring the selenium precursor solution into a second mixed solution, and stirring for 20-40min at 180-250 ℃ in a nitrogen atmosphere; adding the cation solution, stirring for 10-30min, cooling to room temperature, and centrifuging with high speed centrifuge to obtain pure Sb2Se3The antimony selenide nanorod is 50-300 nm in length;
wherein 0.5-2mmol of antimony trichloride is added to every 5mL of triethylene glycol; the composition of the first mixed solution is monoethanolamine and N2H4·H2O, the volume ratio of the two is 4:1, and 1-2mmol of selenium powder is added into each 1.5mL of the first mixed solution; the second mixed solution consists of polyvinylpyrrolidone and triethylene glycol, wherein 0.1g of polyvinylpyrrolidone is added in each 20ml of triethylene glycol; volume ratio cationic solution: selenium precursor solution: the second mixed solution is 5: 1-2: 10-30 parts of;
second, prepare antimony selenide/sulfur (Sb)2Se3/S) composite lithium-sulfur battery positive electrode material:
grinding the antimony selenide nano-rods and the sulfur powder prepared in the previous step in a mortar for 10-30min, and then placing the ground antimony selenide nano-rods and the sulfur powder in a ventilated kitchen for dropwise adding CS2Grinding until no elemental sulfur is separated out, putting the material into an inner container of a polytetrafluoroethylene reaction kettle under the atmosphere of argon, reacting for 10-16h at the temperature of 150-160 ℃, and finally cooling to room temperature to prepare the antimony selenide/sulfur composite material, namely the lithium-sulfur battery positive electrode material;
wherein the mass ratio is antimony selenide nanorod: 1: 2-4 of sulfur powder;
the rotating speed of the high-speed centrifuge is 6000 rap/min.
2. The use of the positive electrode material for lithium-sulfur batteries according to claim 1, characterized by being used as a positive electrode sheet for button cells.
3. The use of the positive electrode material for a lithium-sulfur battery according to claim 2, characterized by comprising the steps of:
the preparation method comprises the steps of placing antimony selenide/sulfur composite material, conductive carbon black and polyvinylidene fluoride in a mortar according to a medium weight ratio of 8:1:1 for mixing and grinding, then dropping N-methyl pyrrolidone for continuous grinding to form bright black slurry, coating the slurry on an aluminum foil with the coating thickness of 10-30 mu m, drying the slurry in a drying oven at 60 ℃ for 12 hours, then punching the sheet into circular sheets with corresponding diameters by using a die, placing the circular sheets under a tablet press for pressure maintaining for 2min, finally placing the circular sheets in a glove box, and assembling the battery according to the sequence of a positive electrode shell, an electrode plate, a diaphragm, electrolyte, a metal lithium sheet, a gasket, a spring piece and a negative electrode shell to assemble the button battery.
CN201810358646.5A 2018-04-20 2018-04-20 Lithium-sulfur battery positive electrode material and application thereof Active CN108550818B (en)

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