CN107808955B - Activated carbon material with spherical structure and preparation method and application thereof - Google Patents
Activated carbon material with spherical structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an activated carbon material with a spherical structure, which is prepared by ultrasonically dispersing saccharides and carbon materials in a mass ratio of 1-5: 1, performing spray pyrolysis treatment and carbonizing. Spherical activated carbon materials are prepared through an ultrasonic spray pyrolysis method, and the carbon materials are used as active material carriers for the positive electrode materials of the lithium-sulfur batteries. The activated carbon material with the spherical structure prepared by the invention is of the spherical structure formed by self-supporting of the carbon material, and the spherical structure has the advantages of large specific surface area and good dispersibility due to the gaps in the sphere, so that the electrochemical performance of the anode material can be effectively improved. The preparation method is simple to operate, low in cost, energy-saving and environment-friendly, and the prepared active carbon material is rich in pore structure, high in electrochemical specific capacity, excellent in cycle performance, stable in structure and environment-friendly when being used as an active substance carrier in a lithium sulfur battery.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to an activated carbon material with a spherical structure and a preparation method and application thereof.
Background
Along with the increasing consumption demand of world energy, the exploitable and utilizable petroleum resources are increasingly exhausted, and the environmental pollution is increasingly serious, so that the storage and the reutilization of clean solar energy and wind energy by utilizing an electrochemical energy storage technology are undoubtedly the most effective way for solving the problem in the 21 st century by human beings; in addition, mobile electronic equipment, electric automobiles and the like which influence the life of people also put higher requirements on future electrochemical energy storage technologies. These are all realized in the need of a safe, inexpensive, high energy density and long-life secondary battery. Among many energy storage modes, lithium ion batteries occupy a central position in the energy storage industry today due to the advantages of light weight, high capacity, no memory effect, and the like.
The lithium ion battery uses graphite material as a negative electrode, lithium-containing metal oxides such as lithium iron phosphate, lithium cobaltate, lithium manganate and the like as a positive electrode, and utilizes the rocking chair effect of lithium ions between the positive electrode and the negative electrode to contribute to capacity, the theoretical specific capacity of the conventional secondary lithium ion battery is nearly 300mAh/g, even if the theoretical specific capacity is difficult to meet the requirement of the secondary battery required by people, and meanwhile, the fuel cell is difficult to be practical in a short time, so the lithium sulfonium battery with the theoretical specific capacity of 1650mAh/g becomes the most attractive secondary battery system at present.
The lithium matte battery takes elemental sulfur as a positive electrode and metal lithium as a negative electrode, wherein the theoretical specific energy of the elemental sulfur reaches 2600Wh/kg, the elemental sulfur is low in price and rich in resources, is environment-friendly, and can replace a lithium ion battery to a certain extent, but the actual specific capacity of the lithium matte battery is far less than the theoretical specific capacity, so that the large-scale application of the lithium matte battery is limited. The main reason for this phenomenon is that during the charge and discharge cycles of the lithium-sulfur battery, the polysulfide is easily dissolved in the electrolyte, and when the cycles are terminated, it is not completely converted into the final product, resulting in the loss of the effective substances, and at the same time, the capacity of the lithium-sulfonium battery is greatly reduced due to the "shuttle effect" caused by the dissolution of the polysulfide. Therefore, the invention of the cathode material capable of improving the shuttle flying effect of the lithium matte battery is very urgent.
Due to a series of defects of elemental sulfur as a cathode material, researchers have most commonly studied the carbon material and elemental sulfur compound as a cathode active material. The carbon material has good conductivity, and the structure of the carbon material can also inhibit migration and diffusion of polysulfide. Carbon materials commonly used in recent years as research targets include: acetylene black, graphene, carbon nanotubes, hollow carbon, porous carbon and the like, which improve and increase the discharge capacity and cycle efficiency of the lithium-sulfur battery to different degrees. The hollow carbon spheres and the carbon tubes have larger internal space, can contain the multi-elemental sulfur and the electrolyte, and inhibit the charge-discharge reaction in the inner cavity, so that the polysulfide is difficult to separate from the carbon shell.
According to the prior art, the discharge capacity and the cycle efficiency of the lithium-sulfur battery prepared by using the carbon material are different, so that the high quality of the lithium-sulfur battery is difficult to ensure. The prepared activated carbon material has different shapes, the consistency is difficult to ensure, and the continuous production of a one-step method is not realized in the production process. And the synthesis of the activated carbon material with a spherical structure by an ultrasonic spray pyrolysis method is not found for a while.
Disclosure of Invention
The invention aims to provide an activated carbon material with a spherical structure, which has high specific capacity, excellent cycle performance, stable structure and environmental friendliness, and has the advantages of good appearance, high specific surface area, large porosity and good adsorbability; the preparation method of the spherical activated carbon has low preparation cost and simple process, can be used for continuously producing the spherical activated carbon, is used as an active substance carrier to be applied to a lithium-sulfur battery, and has the advantages of high electrochemical specific capacity, excellent cycle performance, stable structure, environmental friendliness, good appearance of the activated carbon material, high specific surface area, large porosity and good adsorbability; the spherical active carbon has low preparation cost and simple process, can be continuously produced, is used as an active substance carrier and applied to the lithium-sulfur battery, does not need to be additionally added with a conductive agent, and increases the content of the active substance of the positive electrode; the electrochemical performance is excellent.
Another object of the present invention is to provide a method for preparing an activated carbon material having a spherical structure.
Another object of the present invention is to provide an application of the above activated carbon material having a spherical structure.
The purpose of the invention is realized by the following technical scheme:
providing an activated carbon material with a spherical structure, wherein the activated carbon material is prepared by ultrasonically dispersing saccharides and carbon materials in a mass ratio of 1-5: 1, performing spray pyrolysis treatment and carbonizing; preferably, the mass ratio of the saccharide to the carbon material is 1: 4.
The active carbon anode material prepared by the method is of a spherical structure, the diameter range of the active carbon anode material is 0.5-2 um, the specific surface area is large, the dispersibility is good, and no agglomeration exists. The special structure can load more elemental sulfur, and prevent polysulfide from being dissolved in electrolyte, so that the shuttle flying effect of the lithium-sulfur battery can be reduced, and the electrochemical performance of the cathode material is improved.
The principle of the invention is as follows: the uniformly mixed saccharides and carbon materials are used as precursor materials in a deionized water solution, the precursor materials are condensed into round balls due to surface tension after ultrasonic atomization, the saccharides are used as a binder, and in the spray pyrolysis process, heating water is evaporated, and the materials form the activated carbon composite material with a spherical structure.
Further, the saccharide is at least one of sucrose, glucose and fructose.
Further, the carbon material is at least one of graphene, carbon nanotubes, acetylene black, carbon black, and carbon fibers.
The active carbon material provided by the invention has the hollow carbon spheres and the carbon tubes with larger internal space, can contain multi-simple substance sulfur and electrolyte, and inhibits charge-discharge reaction in the inner cavity, so that polysulfide is difficult to separate from a carbon shell.
The invention provides a preparation method of an activated carbon material with a spherical structure, which comprises the following steps:
s1, ultrasonic dispersion: mixing saccharides and a carbon material in a deionized water solution, wherein the mass ratio of the total mass of the saccharides and the carbon material to the deionized water is 1: 30-40; stirring the total mass of the saccharides and the carbon material for 3-8 hours at room temperature by using deionized water, and then performing ultrasonic dispersion by using an electromagnetic ultrasonic device, wherein the power of the ultrasonic dispersion is 200-750W; the ultrasonic dispersion time is 0.5-2 h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: atomizing the mixed solution obtained in the step S1 through an ultrasonic atomizer, wherein the atomizing flow rate is 200-300cc/min, introducing the atomized mixed solution into a vacuum tube furnace which is pre-filled with inert gas, carrying out constant temperature treatment, preheating to 350-450 ℃, and carrying out heat preservation for 24-36 h; keeping the temperature constant until the spraying is finished, continuing for 2 hours, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonizing: s2, grinding the product deposited in the tube, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; after the mixture is sieved by a sieve of 100-300 meshes, the mixture is put into a vacuum tube furnace filled with inert gas, the temperature is raised to 600-800 ℃, the heat preservation time is 0.5-5 h, and the vacuum tube furnace is cooled to the room temperature; collecting the obtained product to obtain the spherical active carbon material.
Further preferably, the mixing and stirring time of the saccharides and the carbon material is 3-5 h; the power of ultrasonic dispersion is 500-600W.
Further preferably, the temperature rise rate of the reaction furnace for the spray pyrolysis treatment in step S2 is 5 to 10 ℃/min.
Further preferably, the temperature rise speed of the vacuum tube furnace in the step S3 is 5-10 ℃/min, and the heat preservation time is 2-4 h.
Further preferably, the inert gas is one of nitrogen and argon.
Another object of the present invention is to provide the use of an activated carbon material having a spherical structure for the preparation of a positive electrode for a lithium-sulfur battery.
The invention also aims to provide the activated carbon material with the spherical structure, which is used in the fields of catalyst carriers, water treatment, sewage purification and solvent adsorption.
The carbon material of the present invention is derived from carbohydrates and other carbon materials commonly found in laboratories. Mixing and stirring saccharide substances and other carbon materials, and ultrasonically dispersing by using an electromagnetic ultrasonic device. And (3) placing the dispersed mixed solution in a special container, spraying the mixed solution into an electromagnetic vacuum tube furnace through an ultrasonic sprayer, and carbonizing under the protection of high-purity argon. And reacting the obtained carbon material with elemental sulfur in a vacuum tube furnace to obtain the carbon/sulfur composite material for the positive electrode of the lithium-sulfur battery. Compared with the conventional carbon material, the lithium-sulfur battery cathode material prepared from the activated carbon material with the spherical structure and the composite material thereof has better appearance and performance, and the preparation method is simple and easy to implement, can realize continuous preparation, is low in cost, is green and environment-friendly, and has good application prospect.
Compared with the prior art, the invention has the following beneficial effects:
the active carbon material with the spherical structure prepared by the invention has the advantages of large specific surface area and better dispersity due to the spherical structure, and can effectively improve the electrochemical performance of the anode material.
The composite material prepared by compounding the activated carbon material with the spherical structure and elemental sulfur is used as the positive electrode material of the lithium-sulfur battery, the first charge-discharge specific capacity reaches 1320mAh/g under the action of 0.1C current density at room temperature, and the first circulating coulombic effect reaches 98%; and the method has good cycle performance, the capacity is still kept 87% after 500 cycles, and the method has good commercial application prospect.
The preparation method of the activated carbon material with the spherical structure is simple to operate, low in cost, energy-saving and environment-friendly, and the prepared activated carbon material is rich in pore structure and large in specific surface area, and has great application prospects in the relevant fields of catalyst carriers, water treatment, sewage purification, solvent adsorption and recovery and the like.
Drawings
FIG. 1 is a scanning electron micrograph of an activated carbon material having a spherical structure according to example 2 of the present invention.
FIG. 2 is a transmission electron micrograph of an activated carbon material having a spherical structure of example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples. The starting materials and methods employed in the examples of the present invention are those conventionally available in the market and conventionally used in the art, unless otherwise specified.
The activated carbon material with the spherical structure is prepared by performing spray pyrolysis treatment and carbonization on saccharides and carbon materials which are subjected to ultrasonic dispersion and have a mass ratio of 1-5: 1. Wherein the saccharide is at least one of sucrose, glucose and fructose; the carbon material is at least one of graphene, carbon nanotubes, acetylene black, carbon black and carbon fibers.
The method comprises the following steps: preparing a saccharide and a carbon material according to a mass ratio of 1-5: 1, dissolving an auxiliary agent in deionized water, performing ultrasonic dispersion, atomizing a dispersed mixed solution through an ultrasonic atomizer, introducing the atomized mixed solution into a reaction furnace, introducing an inert gas into the reaction furnace, and preheating to 350-450 ℃; preserving the heat for 24-36 h; keeping the temperature constant until the spraying is finished, continuing for 2 hours, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature; then grinding and sieving are carried out; and sequentially carrying out high-temperature carbonization in an inert atmosphere to obtain the activated carbon material with the spherical structure.
More specifically:
the preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing and stirring saccharides and carbon materials in a deionized water solution at room temperature for 3-24 hours, and then carrying out ultrasonic dispersion by using an electromagnetic ultrasonic device, wherein the power of the ultrasonic dispersion is 200-750W; the ultrasonic dispersion time is 0.5-10 h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask, atomizing by an ultrasonic atomizer, introducing the atomized mixed solution into a vacuum tube furnace which is pre-filled with inert gas, carrying out constant temperature treatment, pre-heating to 350-450 ℃, and carrying out 24 hours; keeping the temperature constant until the spraying is finished, continuing for 2 hours, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; after the mixture is sieved by a sieve of 100-300 meshes, the mixture is put into a vacuum tube furnace filled with inert gas, the temperature is raised to 600-800 ℃, the temperature is kept for 0.5-5 h, and the vacuum tube furnace is cooled to room temperature; collecting the obtained product to obtain the spherical active carbon material.
The invention is further described below by way of examples.
Example 1
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing sucrose and graphite according to a mass ratio of 4:1, placing the mixture in a deionized water solution, wherein the mass ratio of the total mass of the saccharides and the carbon material to the deionized water is 1:40, mixing and stirring the mixture for 3 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 200W; the ultrasonic dispersion time is 1h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask fixed on an ultrasonic spraying device, atomizing by an ultrasonic sprayer with the flow rate of 200-300cc/min, introducing the atomized mixed solution into an electromagnetic vacuum tube furnace which is pre-filled with argon, heating to 350 ℃ at the heating rate of 5 ℃/min, and carrying out constant-temperature treatment; atomizing by an ultrasonic atomizer for 24 hours; keeping the temperature constant for 2 hours after the spraying solution is completely sprayed, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; sieving with 100 mesh sieve, placing into vacuum tube furnace, heating at 5 deg.C/min for 2 hr, carbonizing at 600 deg.C under the protection of argon gas for 2 hr, and cooling to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the electrode made of the spherical active carbon material are as follows: the prepared composite negative electrode material, acetylene black and PVDF are uniformly mixed in NMP according to the mass ratio of 80:10:10, the mixture is coated on aluminum foil to prepare an electrode, and a metal lithium sheet is taken as a negative electrode to be assembled into a button battery in a glove box. The electrolyte is 1M LiTFSI/DOL-DME (volume ratio is 1:1), and the diaphragm is a celgard 2400 microporous membrane. The cell is subjected to cycle and rate performance test by adopting a new power (fresh) charge-discharge tester, the voltage range of the chemical performance test is 1.7-2.8V, the current density is 0.1C, and the test temperature is 25 ℃. The results of the electrochemical performance tests are shown in table 1.
Example 2
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing sucrose and carbon nanotubes in a mass ratio of 5:1, placing the mixture in a deionized water solution, mixing and stirring the mixture for 6 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 750W; the ultrasonic dispersion time is 0.5h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a two-neck flask fixed on an ultrasonic spraying device, atomizing by an ultrasonic sprayer with the flow rate of 200-300cc/min, introducing the atomized mixed solution into an electromagnetic vacuum tube furnace which is pre-filled with argon, heating to 400 ℃ at the heating rate of 5 ℃/min, and carrying out constant temperature treatment; atomizing by an ultrasonic atomizer for 24 hours; keeping the temperature constant for 2 hours after the spraying solution is completely sprayed, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; sieving with a 300-mesh sieve, placing into a vacuum tube furnace, heating at 10 deg.C/min for 2 hr, carbonizing at 800 deg.C under the protection of argon gas for 5 hr, and cooling to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1. The microstructure of the activated carbon material with a spherical structure obtained in this example was observed, and the scanning electron microscope image and the transmission electron microscope image thereof are respectively shown in fig. 1 and fig. 2. The pictures show that the material is a carbon nano tube winding body similar to a 'wool ball', the carbon nano tubes are wound and woven mutually, and the formed ball structure is used for loading sulfur and is used for a lithium sulfur battery anode, so that the conductivity of the material can be greatly improved. The carbon nano tube has a hollow structure and is mutually wound to form rich pores in the sphere, so that the carbon nano tube has a larger internal space, not only can provide enough space for loading sulfur, but also is very favorable for buffering the volume expansion of the sulfur in the discharging process.
Example 3
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing glucose and graphene according to a mass ratio of 3:1, placing the mixture in a deionized water solution, mixing and stirring the mixture for 8 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 500W; the ultrasonic dispersion time is 5 hours, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask fixed on an ultrasonic spraying device, atomizing by an ultrasonic sprayer with the flow rate of 200-300cc/min, introducing the atomized mixed solution into an electromagnetic vacuum tube furnace which is pre-filled with argon, heating to 300 ℃ at the heating rate of 10 ℃/min, and carrying out constant-temperature treatment; atomizing by an ultrasonic atomizer for 24 hours; keeping the temperature constant for 2 hours after the spraying solution is completely sprayed, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonizing: s2, grinding the product deposited in the tube, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; sieving with 300 mesh sieve, placing into vacuum tube furnace, heating at 10 deg.C/min for 4 hr, carbonizing at 750 deg.C under the protection of argon gas for 0.5 hr, and cooling to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1.
Example 4
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing sucrose and carbon nanotubes in a mass ratio of 4:1, placing the mixture in a deionized water solution, mixing and stirring the mixture for 5 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 500W; the ultrasonic dispersion time is 5 hours, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask fixed on an ultrasonic spraying device, heating the mixed solution to 450 ℃ at a heating rate of 5 ℃/min in an electromagnetic vacuum tube furnace under the protection of argon, and atomizing the mixed solution by an ultrasonic atomizer for 24 hours; after all the solution is sprayed, keeping the temperature constant for 2 hours, and after the reaction furnace is cooled to the room temperature, collecting products deposited in the tube;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; sieving with 100 mesh sieve, placing into vacuum tube furnace, heating at 5 deg.C/min for 2 hr, carbonizing at 750 deg.C under the protection of argon gas for 5 hr, and cooling to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1.
Example 5
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing fructose and carbon nano tubes according to a mass ratio of 4:1, placing the mixture in a deionized water solution, mixing and stirring the mixture for 3 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 500W; the ultrasonic dispersion time is 0.5h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask fixed on an ultrasonic spraying device, heating to 400 ℃ at a heating rate of 5 ℃/min in an electromagnetic vacuum tube furnace under the protection of argon, and atomizing by an ultrasonic sprayer for 24 hours; after all the solution is sprayed, keeping the temperature constant for 2 hours, and after the reaction furnace is cooled to the room temperature, collecting products deposited in the tube;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; after being sieved by a 200-mesh sieve, the mixture is put into a vacuum tube furnace, the material is carbonized at 750 ℃ under the protection of argon, the heat preservation time is 2 hours, and the vacuum tube furnace is cooled to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1.
Example 6
(1) Preparation method of activated carbon material with spherical structure
The preparation method of the activated carbon material with the spherical structure comprises the following steps:
s1, ultrasonic dispersion: mixing glucose, carbon nanotubes and graphene according to a mass ratio of 3:1, placing the mixture in a deionized water solution, mixing and stirring the mixture for 12 hours at room temperature by using an electromagnetic stirrer, and performing ultrasonic dispersion by using an electromagnetic ultrasonic device under the power of 500W; the ultrasonic dispersion time is 0.5h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: placing the mixed solution obtained in the step S1 in a double-mouth flask fixed on an ultrasonic spraying device, heating to 400 ℃ at a heating rate of 5 ℃/min in an electromagnetic vacuum tube furnace under the protection of argon, and atomizing by an ultrasonic atomizer for 24 hours; after all the solution is sprayed, keeping the temperature constant for 2 hours, and after the reaction furnace is cooled to the room temperature, collecting products deposited in the tube;
s3, carbonizing: grinding the product deposited in the tube in the step S2, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; after being sieved by a 200-mesh sieve, the mixture is put into a vacuum tube furnace, the material is carbonized at 750 ℃ under the protection of argon, the heat preservation time is 2 hours, and the vacuum tube furnace is cooled to room temperature; collecting the obtained product to obtain the spherical active carbon material.
(2) Application of activated carbon material with spherical structure in positive electrode material of lithium sulfonium battery
And mixing the spherical activated carbon material prepared after carbonization with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and calcining the calcined mixture at 300 ℃ for 1 hour to prepare the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1.
Comparative example 1
The application number is CN201310464652.6, and discloses a positive electrode material containing the additive and a preparation method thereof, the additive provided in the comparison is a composite material of Glucose (Glucose) and Super P (or activated carbon, acetylene black and carbon black), and the preparation method is as follows: 1g of Super P and 5g of glucose are dispersed in 80mL of deionized water, ultrasonically dispersed for 10min in an ultrasonic cleaner, transferred to a 100mL hydrothermal reaction kettle and reacted for 48h at 160 ℃. After the reaction is finished, carrying out suction filtration, drying at 65 ℃, grinding to obtain a composite material of glucose and Super P, namely an additive, mixing the additive with elemental sulfur according to the mass ratio of 2:3, calcining the mixture in a vacuum tube furnace at 155 ℃ for 12 hours, and then calcining the mixture at 300 ℃ for 1 hour to obtain the lithium sulfonium battery anode material.
The preparation and performance test of the lithium sulfonium battery anode material are the same as those in example 1, and the electrochemical performance test results are shown in table 1.
TABLE 1 electrochemical Properties of Sulfur-carbon composite cathode Material having spherical Structure
Claims (6)
1. The activated carbon material with the spherical structure is characterized by being prepared by ultrasonically dispersing saccharides and carbon materials in a mass ratio of 1-5: 1, performing spray pyrolysis treatment and carbonizing, and comprises the following steps:
s1 ultrasonic dispersion: mixing saccharides and a carbon material in a deionized water solution, wherein the mass ratio of the total mass of the saccharides and the carbon material to the deionized water is 1: 30-40; stirring the total mass of the saccharides and the carbon material for 3-8 hours at room temperature by using deionized water, and then performing ultrasonic dispersion by using an electromagnetic ultrasonic device, wherein the power of the ultrasonic dispersion is 200-750W; the ultrasonic dispersion time is 0.5-2 h, and a mixed solution is obtained;
s2, spray pyrolysis treatment: atomizing the mixed solution obtained in the step S1 through an ultrasonic atomizer, wherein the atomizing flow rate is 200-300cc/min, introducing the atomized mixed solution into a vacuum tube furnace which is pre-filled with inert gas, carrying out constant temperature treatment, preheating to 350-450 ℃, and carrying out heat preservation for 24-36 h; keeping the temperature constant until the spraying is finished, continuing for 2 hours, and collecting products deposited in the tube after the reaction furnace is cooled to the room temperature;
s3, carbonization: s2, grinding the product deposited in the tube, wherein the grinding speed is 250-300 r/min, and the grinding time is 2-4 h; after the mixture is sieved by a sieve of 100-300 meshes, the mixture is put into a vacuum tube furnace filled with inert gas, the temperature is raised to 600-800 ℃, the heat preservation time is 0.5-5 h, and the vacuum tube furnace is cooled to the room temperature; collecting the obtained product to obtain a spherical activated carbon material;
wherein the saccharide is at least one of sucrose, glucose and fructose; the carbon material is at least one of graphene, carbon nanotubes, acetylene black, carbon black and carbon fibers.
2. The activated carbon material with a spherical structure according to claim 1, wherein the mixing and stirring time of the saccharides and the carbon material is 3-5 h; the power of ultrasonic dispersion is 500-600W.
3. The activated carbon material with a spherical structure according to claim 1, wherein the temperature rise rate of the reaction furnace in the spray pyrolysis treatment in step S2 is 5-10 ℃/min.
4. The activated carbon material with a spherical structure according to claim 1, wherein the temperature rise rate of the vacuum tube furnace in step S3 is 5-10 ℃/min, and the holding time is 2-4 h.
5. The activated carbon material having a spherical structure according to claim 1, wherein the inert gas is one of nitrogen and argon.
6. Use of the activated carbon material having a spherical structure according to claim 1 for the preparation of a positive electrode for a lithium-sulfur battery.
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| CN108556105A (en) * | 2018-05-18 | 2018-09-21 | 大连门庭木业有限公司 | Environment-friendlycomposite composite board and preparation method thereof with function of absorbing formaldehyde |
| CN111370671B (en) * | 2020-03-20 | 2022-11-04 | 东莞东阳光科研发有限公司 | Preparation method of lithium-sulfur battery positive electrode material |
| CN111640951B (en) * | 2020-05-25 | 2022-10-11 | 湖南西瑞尔新材料科技有限公司 | Preparation method and application of air electrode catalyst layer |
| CN112216839A (en) * | 2020-09-16 | 2021-01-12 | 中国科学院山西煤炭化学研究所 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
| CN112427016B (en) * | 2020-11-23 | 2023-05-02 | 南通市金达菱新材料科技有限公司 | Silver-loaded porous carbon microsphere and preparation method thereof |
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