CN109755531B - Porous carbon-sulfur composite material based on acid horn shell and preparation method and application thereof - Google Patents
Porous carbon-sulfur composite material based on acid horn shell and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a porous carbon-sulfur composite material based on an acid angle shell, a preparation method and application thereof, and the porous carbon-sulfur composite material comprises the following steps: 1. soaking tamarind shell in strong alkali solution, washing with strong acid solution to neutrality, drying in oven, and pulverizing; 2. flatly paving the tamarind powder in a corundum crucible, putting the corundum crucible into a tubular furnace, heating and preserving heat, and naturally cooling the corundum crucible and the corundum crucible to room temperature along with the furnace to obtain pretreated tamarind shell carbon; 3. adding the acid hornshell carbon into an activating agent solution, stirring and activating, and then placing in a drying oven for drying; heating from room temperature, keeping the temperature, completely carbonizing, and naturally cooling to room temperature; 4. putting the product into a strong acid solution to make the product neutral; drying to obtain porous carbon; 5. uniformly mixing porous carbon and sulfur powder, heating and preserving heat, naturally cooling to room temperature along with a furnace, and taking out to obtain the porous carbon-sulfur composite material; the composite material obtained by the invention is used as a positive electrode material to be applied to a lithium-sulfur battery, and the cycling stability of the battery is effectively improved.
Description
Technical Field
The invention belongs to the technical field of preparation of energy storage materials and lithium-sulfur battery positive electrode materials, and particularly relates to a preparation method of a porous carbon-sulfur composite material based on an acid angle shell and application of the porous carbon-sulfur composite material in a lithium-sulfur battery positive electrode material.
Background
With social progress and scientific and technological development, people have increasingly increased demand for energy, traditional fossil fuels such as coal, petroleum, natural gas and other non-renewable energy sources are increasingly exhausted, and research and development and utilization of renewable clean energy sources are more and more concerned by people. Among them, new energy sources such as solar energy, tidal energy, wind energy, geothermal energy, nuclear energy and the like are widely developed and utilized, but how to effectively store and convert the energy and realize environmental friendliness, safety and high efficiency is a problem to be solved urgently. The lithium-sulfur battery has the advantages of low price, environmental friendliness, rich sulfur storage capacity and the like, has high theoretical specific capacity (1675mAh/g) and high energy density (2600Wh/kg), and is known to be the most ideal substitute of the lithium-ion battery in the future. However, there are still many problems to be solved urgently in the current lithium-sulfur battery: 1) due to the existence of the intermediate product lithium polysulfide, a shuttle effect can be generated, so that the coulomb efficiency is low, and the self-discharge is high; 2) during the charging and discharging process, the structural change and the volume expansion can generate lithium dendrite to puncture the diaphragm; 3) sulfur has poor conductivity, increasing the internal resistance of the cell, resulting in lower cycling capability and rate capability.
At present, in order to solve the above problems, the following methods are generally adopted: by using porous carbon to block and adsorb polysulfide ions, the dissolution loss of the polysulfide ions is reduced; doping nitrogen; and the use of catalysts to suppress the shuttling effect, achieving effective "sulfur fixation". Among them, the porous carbon material based on biomass has advantages of easily available material, low cost, environmental friendliness, and the like, and has received more and more attention. Porous carbons based on biomass, such as those obtained from banana peels, chestnut shells, bamboo shoot shells, and the like, have been reported to be applied to lithium ion batteries, sodium ion batteries, and supercapacitors. However, when the porous carbon based on biomass is applied to a lithium ion battery, the problems of poor cycle performance, low first-turn capacity and the like still exist, and the wide application of the porous carbon based on biomass is limited.
Disclosure of Invention
The invention provides a porous carbon-sulfur composite material based on an acid angle shell, a preparation method thereof and application of the porous carbon-sulfur composite material to a lithium-sulfur battery positive electrode material, aiming at the defects in the background art. According to the invention, tamarind shells are used as a biomass source, a porous carbon material is prepared through a series of activation reactions, and then the porous carbon material is compounded with sulfur to obtain a carbon-sulfur composite material, so that the carbon-sulfur composite material has a good sulfur fixing effect, effectively improves the charge and discharge capacity, the cycling stability and the coulombic efficiency of the lithium-sulfur battery, and has a good application prospect.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a porous carbon-sulfur composite material based on an acid angle shell comprises the following steps:
step 2, flatly paving the tamarind powder obtained in the step 1 in a corundum crucible, then putting the corundum crucible into a tubular furnace, heating the mixture to 300-600 ℃ from room temperature under the atmosphere of inert gas, preserving the heat for 1-3 hours, naturally cooling the mixture to room temperature along with the furnace after calcination is completed, and taking the mixture out to obtain pretreated tamarind shell carbon;
step 3, adding the tamarind shell carbon obtained in the step 2 into 1-5 mol/L of an activator solution, stirring and activating for 8-12 hours, pouring the obtained reaction liquid into a corundum crucible, and then placing the corundum crucible into an oven to be dried for 3-12 hours at the temperature of 80-150 ℃ so as to remove water in the corundum crucible; placing the dried product in a tubular furnace, heating the product from room temperature to 500-1000 ℃ under the atmosphere of inert gas, preserving the heat for 1-5 hours to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is finished, and taking the product out;
step 4, putting the product obtained in the step 3 into a strong acid solution with the same concentration as the strong acid solution in the step 1 to make the product neutral; after the completion, drying in a vacuum oven to obtain porous carbon;
and 5, mixing the porous carbon obtained in the step 4 with sulfur powder according to a mass ratio of 1: (1.5-4), uniformly mixing, placing in a tubular furnace, heating from room temperature to 155-300 ℃ under the atmosphere of inert gas, preserving heat for 12-24 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material.
Preferably, the strong alkali solution in the step 1 is an aqueous solution of sodium hydroxide or potassium hydroxide; the strong acid solution is hydrochloric acid, sulfuric acid or nitric acid solution; the ball milling frequency is 31.66 Hz-37.66 Hz.
Preferably, the inert gas in the step 2 is argon; the roasting temperature is 300-500 ℃, and the roasting time is 1-3 h. The roasting temperature and time have important influence on products, too high temperature or too long time can cause over-sufficient carbonization and decrease the carbon yield, and too low temperature or too short time can cause insufficient carbonization of materials, thus being not beneficial to later-stage activation.
Preferably, the activator solution in the step 3 is a potassium hydroxide aqueous solution, a zinc chloride aqueous solution or a phosphoric acid aqueous solution, and the concentration of the activator solution is 1-5 mol/L. A large number of tests show that the activating agents have good activating effects on biomass, can activate the biomass into porous carbon with uniformly distributed pores efficiently, and further endow the composite material with good performance.
Step 3, roasting at 500-1000 ℃ for 1-5 h; the number and size of porous carbon pores are positively correlated with the roasting time, the roasting temperature and the concentration of the activator to a certain extent, however, when the roasting time is too long, the roasting temperature is too high or the concentration of the activator is too high, the pores of the activated carbon material primary product are too large, the specific surface is reduced, and the performance of the battery is influenced.
Preferably, the inert gas in step 3 is argon.
Preferably, the strong acid solution in step 4 is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution. The strong acid can effectively remove metal impurities and oxide impurities, the reaction is sensitive, the reaction speed is high, the efficiency is high, the performance of the carbon material cannot be influenced, and the later-stage removing process is simple.
Preferably, in the step 4, the drying temperature in the vacuum oven is 60-100 ℃, and the drying time is 8-12 h.
Preferably, the temperature rise rate in the temperature rise process from room temperature in the inert gas atmosphere in the step 2, the step 3 and the step 5 is 2-5 ℃/min.
In order to achieve the aim, the invention also provides a porous carbon-sulfur composite material based on the acid angle shell, which is obtained by the preparation method.
In order to achieve the aim, the invention also provides application of the porous carbon-sulfur composite material based on the acid angle shell to a positive electrode material of a lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the tamarind shell is used as a biomass source and is used for synthesizing the carbon-sulfur composite material of the lithium-sulfur battery for the first time, the biomass material contains abundant cellulose and cell tissues, so that the carbon-sulfur composite material has a good supporting effect, and after being compounded with sulfur, the carbon-sulfur composite material has a good sulfur fixing effect; the obtained composite material is used as a positive electrode material to be applied to the lithium-sulfur battery, and the cycling stability of the battery is effectively improved.
2. The carbon-sulfur composite material obtained by the invention has good cycle performance and rate capability and has good application prospect.
3. The method provided by the invention is simple, low in cost and suitable for large-scale industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of the porous carbon obtained in step 4 of example 1 and the porous carbon-sulfur composite material finally obtained;
FIG. 2 is a scanning electron micrograph of the porous carbon obtained in step 4 of example 2; wherein, (a) is SEM picture of 5um, and (b) is SEM picture of 20 um;
FIG. 3 is a scanning electron micrograph of a porous carbon-sulfur composite obtained in example 2; wherein, (a) is SEM picture of 5um, (b) is SEM picture of 10um, (c) is SEM picture of 100um, and (d) is SEM picture of 100 um;
FIG. 4 is a thermogravimetric plot of the porous carbon-sulfur composite obtained in example 3;
fig. 5 is a charge-discharge cycle diagram of the first cycle of the porous carbon-sulfur composite positive electrode material obtained in example 1 at a current density of 0.1C;
fig. 6 is a 300-cycle long cycle plot of the porous carbon-sulfur composite positive electrode material obtained in example 1 at a current density of 0.5C;
fig. 7 is a graph of rate capability of the porous carbon-sulfur composite cathode material obtained in example 1.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
FIG. 1 is an X-ray diffraction pattern of the porous carbon and carbon/sulfur composite obtained in example 1; the G and D peaks of the porous carbon and carbon sulfur composite can be seen from the positions of the peaks in the figure.
FIG. 2 is a scanning electron micrograph of the porous carbon obtained in example 2; wherein, (a) is SEM picture of 5um, and (b) is SEM picture of 20 um; as can be seen from fig. 2, the porous carbon obtained in example 2 has significant wrinkles and pores, and a large specific surface area, which is favorable for sulfur loading and polysulfide adsorption.
FIG. 3 is a scanning electron micrograph of a porous carbon-sulfur composite obtained in example 2; wherein, (a) is SEM picture of 5um, (b) is SEM picture of 10um, (c) is SEM picture of 100um, and (d) is SEM picture of 100 um; as can be seen from fig. 3, the porous carbon-sulfur composite material obtained in example 2 has no significant sulfur particles, which indicates that the sulfur completely enters into the pores of the porous carbon, and the wrinkles and pores of the porous carbon are covered and filled with the sulfur.
FIG. 4 is a thermogravimetric plot of the porous carbon-sulfur composite obtained in example 1; as can be seen from fig. 5, the sulfur content of the porous carbon-sulfur composite material obtained in example 3 was 75.05%, and the porous carbon-sulfur composite material had a high sulfur loading.
Fig. 5 is a first-turn charge-discharge curve of the porous carbon/sulfur composite positive electrode material obtained in example 1 at a current density of 0.1C; as can be seen from FIG. 6, the first cycle discharge capacity is as high as 1382.9mAh/g, and the specific capacity is very high.
Fig. 6 is a long cycle plot of 300 cycles of the porous carbon/sulfur composite positive electrode material obtained in example 1 at a current density of 0.5C;
fig. 7 is a graph of rate capability of the porous carbon/sulfur composite cathode material obtained in example 1; as can be seen from fig. 7, the lithium sulfur battery thus prepared has good cycle performance at a rate of 0.1C,0.2C,0.5C,1C, 2C.
Example 1
A preparation method of a porous carbon-sulfur composite material based on an acid angle shell comprises the following steps:
Step 2, flatly paving the tamarind powder obtained in the step 1 in a corundum crucible, then placing the corundum crucible into a tubular furnace, keeping the temperature of the corundum crucible at 300 ℃ from room temperature at a heating rate of 2 ℃/min under the nitrogen atmosphere, keeping the temperature for 1 hour, naturally cooling the corundum crucible to room temperature along with the furnace after calcination is completed, and taking out the corundum crucible to obtain pretreated tamarind shell carbon;
step 3, adding the pretreated tamarind shell carbon obtained in the step 2 into 1mol/L potassium hydroxide aqueous solution, stirring and activating for 8 hours, pouring the obtained reaction liquid into a corundum crucible, and then drying for 3 hours in an oven at the temperature of 80 ℃ to remove moisture in the corundum crucible; placing the dried product in a tubular furnace, heating the product from room temperature to 500 ℃ at a heating rate of 2 ℃/min under the atmosphere of argon, preserving the heat for 1h to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is finished, and taking the product out;
step 4, putting the product obtained in the step 3 into a strong acid solution with the same concentration as the strong acid solution in the step 1 to enable the product to be neutral, and after the product is finished, drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain porous carbon;
and 5, mixing the porous carbon obtained in the step 4 with sulfur powder according to a mass ratio of 2: 3, uniformly mixing, placing in a tubular furnace, heating to 155 ℃ from room temperature at a heating rate of 2 ℃/min under an inert gas atmosphere, preserving heat for 12 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material; the porous carbon-sulfur composite material can be directly used as a lithium-sulfur battery cathode material.
Example 2
A preparation method of a porous carbon-sulfur composite material based on an acid angle shell comprises the following steps:
Step 2, flatly paving the tamarind powder obtained in the step 1 in a corundum crucible, then placing the corundum crucible into a tubular furnace, heating the mixture to 600 ℃ from room temperature at a heating rate of 3 ℃/min under the nitrogen atmosphere, preserving heat for 3 hours, naturally cooling the mixture to room temperature along with the furnace after the heating is finished, and taking the mixture out to obtain pretreated tamarind shell carbon;
step 3, adding the pretreated tamarind shell carbon obtained in the step 2 into a 5mol/L potassium hydroxide aqueous solution, stirring and activating for 12 hours, pouring the obtained reaction liquid into a corundum crucible, and then placing the corundum crucible in an oven to dry for 12 hours at the temperature of 150 ℃ so as to remove moisture in the corundum crucible; placing the dried product in a tubular furnace, heating the product from room temperature to 1000 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, preserving the heat for 5 hours to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is finished, and taking the product out;
step 4, putting the product obtained in the step 3 into a hydrochloric acid solution of 3mol/L to make the product neutral, and after the product is finished, drying the product in a vacuum oven for 8 hours at the temperature of 80 ℃ to obtain porous carbon;
and 5, mixing the porous carbon obtained in the step 4 with sulfur powder according to a mass ratio of 1: 4, uniformly mixing, placing in a tubular furnace, heating from room temperature to 300 ℃ at a heating rate of 3 ℃/min under an inert gas atmosphere, preserving heat for 24 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material. The porous carbon-sulfur composite material can be directly used as a lithium-sulfur battery cathode material.
Example 3
A preparation method of a porous carbon-sulfur composite material based on an acid angle shell comprises the following steps:
Step 2, flatly paving the tamarind fruit powder obtained in the step 1 in a corundum crucible, then placing the corundum crucible into a tubular furnace, heating the mixture to 450 ℃ from room temperature at a heating rate of 4 ℃/min under the nitrogen atmosphere, preserving heat for 2 hours, naturally cooling the mixture to room temperature along with the furnace after the heating is finished, and taking the mixture out to obtain pretreated tamarind fruit shell carbon;
step 3, adding the pretreated tamarind shell carbon obtained in the step 2 into 3mol/L zinc chloride aqueous solution, stirring and activating for 10 hours, pouring the obtained reaction liquid into a corundum crucible, and then drying for 9 hours in a drying oven at 120 ℃ to remove moisture in the corundum crucible; placing the dried product in a tube furnace, heating the product from room temperature to 800 ℃ at a heating rate of 4 ℃/min under the argon atmosphere, preserving the heat for 3 hours to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is completed, and taking the product out;
and 4, putting the product obtained in the step 3 into a 2mol/L sulfuric acid solution to enable the product to be neutral, and after the product is finished, drying the product in a vacuum oven for 10 hours at the temperature of 100 ℃ to obtain the porous carbon.
And 5, setting the mass ratio of the porous carbon obtained in the step 4 to the sulfur powder as 2: 5, uniformly mixing, placing in a tubular furnace, heating from room temperature to 220 ℃ at a heating rate of 4 ℃/min under an inert gas atmosphere, preserving heat for 20 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material. The porous carbon-sulfur composite material can be directly used as a lithium-sulfur battery cathode material.
Example 4
A preparation method of a porous carbon-sulfur composite material based on an acid angle shell comprises the following steps:
Step 2, flatly paving the tamarind fruit powder obtained in the step 1 in a corundum crucible, then placing the corundum crucible into a tubular furnace, heating the mixture to 550 ℃ from room temperature at a heating rate of 5 ℃/min under the nitrogen atmosphere, preserving heat for 2 hours, naturally cooling the mixture to room temperature along with the furnace after the heating is finished, and taking the mixture out to obtain pretreated tamarind fruit shell carbon;
step 3, adding the pretreated tamarind shell carbon obtained in the step 2 into a 4mol/L phosphoric acid aqueous solution, stirring and activating for 11 hours, pouring the obtained reaction liquid into a corundum crucible, and then drying in an oven at 100 ℃ for 6 hours to remove moisture in the corundum crucible; placing the dried product in a tubular furnace, heating the product from room temperature to 900 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 4 hours to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is completed, and taking the product out;
and 4, putting the product obtained in the step 3 into a nitric acid solution of 2mol/L to enable the product to be neutral, and drying the product in a vacuum oven at 60 ℃ for 9 hours after the product is finished to obtain the porous carbon.
And 5, setting the mass ratio of the porous carbon obtained in the step 4 to the sulfur powder as 1: 3, uniformly mixing, placing in a tubular furnace, heating to 270 ℃ from room temperature at a heating rate of 5 ℃/min under an inert gas atmosphere, preserving heat for 22 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material; the porous carbon-sulfur composite material can be directly used as a lithium-sulfur battery cathode material.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A preparation method of a porous carbon-sulfur composite material based on an acid angle shell is characterized by comprising the following steps:
step 1, soaking the tamarind shell in 1-3 mol/L strong base solution for 12-24 hours, washing the tamarind shell to be neutral by using strong acid solution with the same concentration as the strong base solution, and removing impurities on the surface of the tamarind shell; putting the cleaned tamarind shells into a drying oven at 50-100 ℃ for drying for 12-24 hours, removing water, and then crushing to millimeter level by using a planetary ball mill for later use; the strong alkali solution in the step 1 is an aqueous solution of sodium hydroxide or potassium hydroxide; the strong acid solution is hydrochloric acid, sulfuric acid or nitric acid solution; the ball milling frequency is 31.66 Hz-37.66 Hz;
step 2, flatly paving the tamarind powder obtained in the step 1 in a corundum crucible, then putting the corundum crucible into a tubular furnace, heating the mixture to 300-600 ℃ from room temperature under the atmosphere of inert gas, preserving the heat for 1-3 hours, naturally cooling the mixture to room temperature along with the furnace after calcination is completed, and taking the mixture out to obtain pretreated tamarind shell carbon;
step 3, adding the tamarind shell carbon obtained in the step 2 into 1-5 mol/L of an activator solution, stirring and activating for 8-12 hours, pouring the obtained reaction liquid into a corundum crucible, and then placing the corundum crucible into an oven to be dried for 3-12 hours at the temperature of 80-150 ℃ so as to remove water in the corundum crucible; placing the dried product in a tubular furnace, heating the product from room temperature to 500-1000 ℃ under the atmosphere of inert gas, preserving the heat for 1-5 hours to completely carbonize the product, naturally cooling the product to room temperature along with the furnace after the carbonization is finished, and taking the product out;
step 4, putting the product obtained in the step 3 into a strong acid solution with the same concentration as the strong acid solution in the step 1 to make the product neutral; after the completion, drying in a vacuum oven to obtain porous carbon; drying in a vacuum oven at 60-100 deg.C for 8-12 h;
and 5, mixing the porous carbon obtained in the step 4 with sulfur powder according to a mass ratio of 1: (1.5-4), uniformly mixing, placing in a tubular furnace, heating from room temperature to 155-300 ℃ under the atmosphere of inert gas, preserving heat for 12-24 hours, naturally cooling to room temperature along with the furnace after the completion, and taking out to obtain the porous carbon-sulfur composite material.
2. The method for preparing a porous carbon-sulfur composite material based on acid angle shells according to claim 1, characterized in that: step 2, the inert gas is argon; the roasting temperature is 300-500 ℃, and the roasting time is 1-3 h.
3. The method for preparing a porous carbon-sulfur composite material based on acid angle shells according to claim 1, characterized in that: and 3, the activating agent solution is a potassium hydroxide aqueous solution, or a zinc chloride aqueous solution, or a phosphoric acid aqueous solution, and the concentration of the activating agent solution is 1-5 mol/L.
4. The method for preparing a porous carbon-sulfur composite material based on acid angle shells according to claim 1, characterized in that: and 3, the inert gas is argon.
5. The method for preparing a porous carbon-sulfur composite material based on acid angle shells according to claim 1, characterized in that: and 4, the strong acid solution is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution.
6. The method for preparing a porous carbon-sulfur composite material based on acid angle shells according to claim 1, characterized in that: in the step 2, the step 3 and the step 5, the temperature rise rate in the temperature rise process from room temperature under the inert gas atmosphere is 2-5 ℃/min.
7. Porous carbon-sulfur composite material based on acid angle shells obtained by the production method according to any one of claims 1 to 6.
8. Use of the acid angle shell based porous carbon-sulfur composite material of claim 7 for a lithium sulfur battery positive electrode material.
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| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN106981644A (en) * | 2017-05-24 | 2017-07-25 | 华中科技大学 | A kind of porous carbon based on biomass/sulphur composite material and preparation method thereof and its application |
| CN108439363A (en) * | 2018-02-26 | 2018-08-24 | 北京理工大学 | Sodium-ion battery hard carbon cathode material based on biomass |
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| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN106981644A (en) * | 2017-05-24 | 2017-07-25 | 华中科技大学 | A kind of porous carbon based on biomass/sulphur composite material and preparation method thereof and its application |
| CN108439363A (en) * | 2018-02-26 | 2018-08-24 | 北京理工大学 | Sodium-ion battery hard carbon cathode material based on biomass |
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