CN116177521A - Preparation method of mesoporous carbon material by efficiently utilizing pore-forming agent - Google Patents
Preparation method of mesoporous carbon material by efficiently utilizing pore-forming agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a mesoporous carbon material by efficiently utilizing a pore-forming agent, which specifically comprises the following steps: step 1, adding a pore-forming agent and a dispersing agent into a solvent for sanding, and then adding a carbon source for continuous sanding to obtain a uniform liquid phase mixture; step 2, drying the liquid phase mixture obtained in the step 1, and calcining the dried powder in an inert atmosphere; and step 3, etching the product obtained by calcining in the step 2 by hydrochloric acid, preserving heat, removing the pore-forming agent, flushing by using ethanol and deionized water, and carrying out suction filtration and drying to obtain the mesoporous carbon material. The invention solves the problems of low utilization rate of pore-forming agent and uneven pore structure distribution in the existing preparation method.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode active material, and relates to a preparation method of a mesoporous carbon material by efficiently utilizing a pore-forming agent.
Background
Mesoporous carbon is widely prepared from one of the following raw materials. Asphalt is an ideal precursor of carbon material, and is low in cost, high in yield and high in carbon content, and is used as an intermediate product in petroleum or coal refining process. In the traditional method, most of asphalt and pore-forming agents are directly ground manually, mixed by ultrasonic stirring and ball-milling, or asphalt is firstly dissolved in tetrahydrofuran and then the pore-forming agents are added for mixing, in the mixing process, the pore-forming agents are difficult to completely disperse and uniformly mixed with the asphalt, the utilization rate of the pore-forming agents is low, and the pore structure is unevenly distributed. Tetrahydrofuran belongs to a volatile toxic solvent, and the subsequent process involves evaporating to dryness, has severe process conditions and causes environmental pollution.
Disclosure of Invention
The invention aims to provide a preparation method of mesoporous carbon material by efficiently utilizing a pore-forming agent, which solves the problems of low utilization rate of the pore-forming agent and uneven pore structure distribution in the existing preparation method.
The technical scheme adopted by the invention is that the preparation method of the mesoporous carbon material efficiently utilizing the pore-forming agent comprises the following steps:
step 1, adding a pore-forming agent and a dispersing agent into a solvent for sanding, and then adding a carbon source for continuous sanding to obtain a uniform liquid phase mixture;
step 2, drying the liquid phase mixture obtained in the step 1, and calcining the dried powder in an inert atmosphere;
and step 3, etching the product obtained by calcining in the step 2 by hydrochloric acid, preserving heat, removing the pore-forming agent, flushing by using ethanol and deionized water, and carrying out suction filtration and drying to obtain the mesoporous carbon material.
The invention is also characterized in that:
in the step 1, the sanding time of the pore-forming agent and the dispersing agent is 1-10h, and the sanding is continued for 1-5h after the carbon source is added, and the solid content of the liquid phase mixed solution is 1% -20%.
In the step 1, the mass ratio of the carbon source to the pore-forming agent is 1 (0.5-10), and the addition amount of the dispersing agent is 1-20wt%.
In the step 2, the calcination process specifically comprises the following steps: under the inert gas atmosphere, the temperature is raised to 250-350 ℃ at the speed of 2-6 ℃/min, the temperature is kept for 0.5-4h, the temperature is raised to 400-600 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 1-6h, and finally the temperature is raised to 800-950 ℃ at the speed of 3-8 ℃/min, and the temperature is kept for 1-6h.
In the step 2, the liquid phase mixture is dried by one of evaporation drying, spray drying and freeze drying.
In the step 3, the concentration of hydrochloric acid used for removing the pore-forming agent is 1-10mol/L, the etching time is more than 24 hours, and the heat preservation temperature is 30-120 ℃.
The invention has the beneficial effects that the invention discloses a preparation method of mesoporous carbon material by using pore-forming agent with high efficiency, which takes high carbon residue precursor as carbon source, and the pore-forming agent, dispersant and asphalt are fully and uniformly mixed by sanding, and then dried, and the obtained powder is calcined and pickled to obtain the mesoporous carbon material. In the preparation method, the particle size of the raw materials is reduced by a sand grinding method, and meanwhile, the pore-forming agent is fully dispersed and uniformly mixed with the carbon source, so that the mixing uniformity of the pore-forming agent and the carbon source is greatly improved compared with solid phase mixing, the utilization rate of the pore-forming agent is improved, and the uniform distribution of mesoporous carbon pore structures is facilitated. Compared with the traditional liquid phase mixing, in the preparation method, the mixed liquid is uniform and has no sediment, and the solvent is volatilized and has no pollution. The mesoporous carbon prepared by the method has proper pore diameter and mesoporous volume, has uniform pore structure distribution, and can be used as a good carbon precursor in a silicon-carbon composite material.
Drawings
FIG. 1 is a flow chart of a method for preparing mesoporous carbon material with efficient use of pore formers according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1 of the method for preparing mesoporous carbon material by efficiently utilizing pore-forming agent according to the present invention;
FIG. 3 is a graph showing the desorption pore diameter of BJH in example 1 of the method for preparing mesoporous carbon material by using pore-forming agent with high efficiency according to the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of comparative example 1 of the inventive mesoporous carbon material preparation method that utilizes a pore-forming agent efficiently;
FIG. 5 is a Scanning Electron Microscope (SEM) image of comparative example 2 of the inventive mesoporous carbon material preparation method that utilizes a pore-forming agent efficiently;
FIG. 6 is a Scanning Electron Microscope (SEM) image before sanding of the calcium carbonate;
fig. 7 is a Scanning Electron Microscope (SEM) image of the calcium carbonate prior to sanding.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The preparation method of the mesoporous carbon material efficiently utilizing the pore-forming agent, as shown in fig. 1, specifically comprises the following steps:
step 1, adding a pore-forming agent and a dispersing agent into a solvent, uniformly mixing, and then adding a carbon source, and mixing to obtain a uniform liquid phase mixture.
The specific operation comprises the following steps: firstly, adding a pore-forming agent and a dispersing agent into a solvent for medium sand grinding for a period of time, and then adding a carbon source for continuous sand grinding to obtain a uniform liquid phase mixture;
wherein, the sanding time of the pore-forming agent and the dispersing agent is 1-10h, the sanding is continued for 1-5h after adding the carbon source, and the solid content of the liquid phase mixed solution is 1% -20%.
The pore-forming agent is at least one of calcium carbonate, magnesium oxide, zinc oxide, potassium hydroxide and zinc chloride, and the dispersing agent is at least one of stearic acid, PVP, oleic acid, ricinoleic acid and n-octanoic acid; the carbon source is at least one of petroleum asphalt, coal asphalt and emulsified asphalt;
the mass ratio of the carbon source to the pore-forming agent is 1 (0.5-10), and the addition amount of the dispersing agent is 1-20wt%.
And 2, drying the mixture obtained in the step 1, and calcining the obtained powder under an inert atmosphere.
In the step 2, the calcination process specifically comprises the following steps: heating to 250-350deg.C at a speed of 2-6deg.C/min under inert gas atmosphere, maintaining for 0.5-4 hr, heating to 400-600deg.C at a speed of 1-5deg.C/min, maintaining for 1-6 hr, and heating to 800-950 deg.C at a speed of 3-8deg.C/min for 1-6 hr; the liquid phase mixture is dried by one of evaporation drying, spray drying and freeze drying.
And 3, etching the product obtained by calcining in the step 2 by hydrochloric acid to remove the pore-forming agent, respectively flushing with ethanol and deionized water for 3-5 times, and performing suction filtration and drying to obtain the mesoporous carbon material.
In the step 3, the concentration of hydrochloric acid used for removing the pore-forming agent is 1-10mol/L, the etching time is more than 24 hours, and the heat preservation temperature is 30-120 ℃.
Example 1
Adding 50g of calcium carbonate and 1g of stearic acid into 500ml of ethanol solution, sanding for 1h, adding 10g of petroleum asphalt, continuing sanding for 1h, placing the powder obtained after spray drying of the liquid phase into a tube furnace, heating to 300 ℃ at a speed of 2 ℃/min under inert gas atmosphere, preserving heat for 2h, heating to 480 ℃ at a speed of 1 ℃/min, preserving heat for 1h, and finally heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 2h; and (3) reacting the collected black powder for 25 hours at the temperature of 80 ℃ with the concentration of hydrochloric acid of 2mol/L, respectively flushing the black powder with ethanol and deionized water for 3 times after no obvious bubbles are generated, and performing suction filtration and drying to obtain the mesoporous carbon.
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1; the SEM result of FIG. 2 shows that the sample has a spherical porous structure, the pore structure has uniform size and distribution, no agglomeration and no pore area, and the uniformity of raw material mixing is good.
FIG. 3 is a BJH desorption pore size distribution plot for example 1; the BJH desorption pore diameter distribution result shows that the pore structure of the material mainly consists of mesopores, the pore volume is mainly distributed at 8-20nm, and the average pore diameter of the mesopores is 13nm.
Example 2
The calcination temperature was 950℃as compared with example 1, and the rest of the steps were the same.
Example 3
The calcium carbonate addition was 20g compared to example 1, the rest of the procedure being identical.
Example 4
Adding 100g of magnesium oxide and 20g of oleic acid into 500ml of ethanol solution, sanding for 10 hours, adding 10g of petroleum asphalt, continuing sanding for 5 hours, placing the powder obtained after spray drying of the liquid phase into a tube furnace, heating to 250 ℃ at a speed of 6 ℃/min under inert gas atmosphere, preserving heat for 0.5 hours, heating to 400 ℃ at a speed of 5 ℃/min, preserving heat for 6 hours, heating to 950 ℃ at a speed of 8 ℃/min, and preserving heat for 1 hour; and (3) reacting the collected black powder for 30 hours at the temperature of 30 ℃ with the concentration of hydrochloric acid of 1mol/L, respectively washing the black powder with ethanol and deionized water for 4 times after no obvious bubbles are generated, and performing suction filtration and drying to obtain mesoporous carbon.
Example 5
Adding 5g of magnesium oxide and 0.05g of oleic acid into 500ml of ethanol solution, sanding for 5 hours, adding 10g of petroleum asphalt, continuing to sand for 3 hours, placing the powder obtained after spray drying of the liquid phase into a tube furnace, heating to 300 ℃ at a speed of 4 ℃/min under inert gas atmosphere, preserving heat for 4 hours, heating to 500 ℃ at a speed of 3 ℃/min, preserving heat for 4 hours, and finally heating to 850 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours; and (3) reacting the collected black powder for 28 hours at the hydrochloric acid concentration of 10mol/L and the temperature of 120 ℃, respectively washing for 5 times by using ethanol and deionized water after no obvious bubbles are generated, and carrying out suction filtration and drying to obtain the mesoporous carbon.
Comparative example 1
Compared with the example 1, the asphalt and the calcium carbonate are subjected to solid phase mixing by adopting a manual grinding mode and then are calcined, and the rest steps are the same.
Comparative example 2
Compared with example 1, asphalt and calcium carbonate are subjected to solid phase mixing by a VC mixer and then calcined, and the rest steps are the same.
The mesoporous carbon materials provided in examples 1 to 3 and comparative examples 1 to 2 were respectively subjected to performance tests, and the test items were: specific surface area, pore volume and pore size.
The mesoporous carbon materials provided in examples 1-3 and comparative examples 1-2 were used to prepare lithium ion battery negative electrode materials, then button-type lithium ion batteries were assembled, and the materials used to assemble the lithium ion batteries were all the same, wherein the positive electrode was a lithium sheet, the current collector was a copper foil, and the first charge specific capacity and the first coulombic efficiency of each group of lithium ion batteries were tested after the assembly was completed. Table 1 below shows the results of comparing the parameters of examples 1 to 3 with those of comparative examples 1 and comparative example 2:
TABLE 1
As can be seen from the above Table 1, the prepared 3 types of mesoporous carbon materials generally have higher specific surface area and mesoporous volume ratio, and the average pore diameter is about 14 nm. The electrochemical performance test results show that example 1 has higher reversible capacity. Comparative examples 1 and 2 and figures 4, 5, 6 and 7 show that the sanding process refines the calcium carbonate template, and simultaneously ensures that the calcium carbonate template is uniformly mixed, thereby remarkably improving the utilization rate of the pore-forming agent.
The mesoporous carbon prepared by the preparation method of the mesoporous carbon material by using the pore-forming agent can be used for lithium ion batteries.
The preparation method of the mesoporous carbon material by efficiently utilizing the pore-forming agent is characterized by comprising the following steps of:
1. the invention provides a preparation method of asphalt-based mesoporous carbon material, which comprises the steps of taking various different asphalts as carbon precursors, adding pore-forming agents and dispersing agents into solvents through sanding to be mixed so as to fully disperse the pore-forming agents, adding the asphalts to be fully and uniformly mixed with the pore-forming agents, then carrying out spray drying, and calcining and pickling the obtained powder to obtain the mesoporous carbon material. In the preparation method, the fully dispersed pore-forming agent and asphalt are fully mixed into a uniform liquid phase, so that the mixing uniformity of the pore-forming agent and the asphalt is greatly improved compared with the solid phase mixing, the utilization rate of the pore-forming agent is improved, and the uniform distribution of mesoporous carbon pore structures is facilitated. Compared with the traditional liquid phase mixing, in the preparation method, the mixed liquid is uniform and has no sediment, and the solvent is volatilized and has no pollution.
2. In the process of adding asphalt sand, the contact area of the pore-forming agent and asphalt is increased, the pore-forming agent and asphalt particles can be further refined, and the mesoporous carbon material with high porosity and uniform pore distribution is obtained after calcination and etching.
Claims (6)
1. The preparation method of the mesoporous carbon material by efficiently utilizing the pore-forming agent is characterized by comprising the following steps of: the method specifically comprises the following steps:
step 1, adding a pore-forming agent and a dispersing agent into a solvent for sanding, and then adding a carbon source for continuous sanding to obtain a uniform liquid phase mixture;
step 2, drying the liquid phase mixture obtained in the step 1, and calcining the dried powder in an inert atmosphere;
and step 3, etching the product obtained by calcining in the step 2 by hydrochloric acid, preserving heat, removing the pore-forming agent, flushing by using ethanol and deionized water, and carrying out suction filtration and drying to obtain the mesoporous carbon material.
2. The method for preparing a mesoporous carbon material efficiently using a pore-forming agent according to claim 1, wherein the method comprises the steps of: in the step 1, the sanding time of the pore-forming agent and the dispersing agent is 1-10h, and the sanding is continued for 1-5h after the carbon source is added, and the solid content of the liquid phase mixed solution is 1% -20%.
3. The method for preparing a mesoporous carbon material efficiently using a pore-forming agent according to claim 2, wherein: in the step 1, the mass ratio of the carbon source to the pore-forming agent is 1 (0.5-10), and the addition amount of the dispersing agent is 1-20wt%.
4. The method for preparing a mesoporous carbon material efficiently using a pore-forming agent according to claim 1, wherein the method comprises the steps of: in the step 2, the calcining process specifically comprises the following steps: under the inert gas atmosphere, the temperature is raised to 250-350 ℃ at the speed of 2-6 ℃/min, the temperature is kept for 0.5-4h, the temperature is raised to 400-600 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 1-6h, and finally the temperature is raised to 800-950 ℃ at the speed of 3-8 ℃/min, and the temperature is kept for 1-6h.
5. The method for preparing a mesoporous carbon material efficiently using a pore-forming agent according to claim 4, wherein the method comprises the steps of: in the step 2, the liquid phase mixture is dried by one of evaporation drying, spray drying and freeze drying.
6. The method for preparing a mesoporous carbon material efficiently using a pore-forming agent according to claim 1, wherein the method comprises the steps of: in the step 3, the concentration of hydrochloric acid used for removing the pore-forming agent is 1-10mol/L, the etching time is more than 24 hours, and the heat preservation temperature is 30-120 ℃.
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