CN114275777A - Preparation method of high-graphitization-degree carbon-based material for lithium battery negative electrode - Google Patents
Preparation method of high-graphitization-degree carbon-based material for lithium battery negative electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-graphitization-degree carbon-based material for a lithium battery cathode, which comprises the following steps of: placing melamine or urea in a porcelain boat, compacting the powder, sealing the porcelain boat with a cover, placing the porcelain boat in a muffle furnace, and slowly heating to obtain carbon nitride powder; dissolving soluble salts of iron, cobalt and nickel in a proper amount of water to obtain a clear solution; placing carbon nitride powder in water, stirring to generate a suspension, dropwise adding the suspension into a clear solution, stirring, performing suction filtration, drying, and treating to obtain a catalyst/carbon nitride powder; crushing the solid asphalt into asphalt powder, and not processing a liquid heavy oil residue precursor; directly mixing the catalyst/carbon nitride powder and the asphalt powder in a solid state; and (3) placing the mixed material in a horizontal tube furnace, slowly heating up under an inert atmosphere, and calcining for 0.5-5h at constant temperature to obtain the product. The invention can obtain thin-layer porous carbon with high graphitization degree, and the thin-layer porous carbon not only has a large amount of graphite with high conductivity, but also has a large amount of cavities for storing lithium.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a high-graphitization-degree carbon-based material for a lithium battery cathode.
Background
With the development of electronic energy storage components in this year, lithium ion batteries are now an indispensable and important part of electric equipment. Lithium battery negative electrodes have carbon-based and non-carbon-based materials. The carbon-based material has excellent physical and chemical stability and conductivity, and is most widely applied, such as artificial graphite, natural graphite and mesocarbon microbeads, which are produced in mass production. However, the capacity of the graphite material is low (the theoretical specific capacity is 372mAh/g) due to the intercalation storage mode of the graphite material, and the rate capability is poor. The graphite layer is easy to fall off in the large-current charging and discharging process. Thus, the low energy density of graphite has not met today's demand for lithium ion power cells. Besides graphite-like carbon negative electrodes, researches on non-carbon negative electrode materials, such as nitrides, silicon-based materials, tin-based materials, novel alloys and the like, are also endless. The highest capacity is obtained by using silicon-based materials (the theoretical specific capacity is 4200 mAh/g). However, during the charging and discharging of silicon as negative electrode of lithium battery, the silicon-lithium alloying step is accompanied by a huge volume effect (volume expansion > 300%), easily causing pulverization of the material, resulting in a short lifetime (not more than several hundred cycles). And the silicon-based material has poor conductivity, so that the development of the silicon-based material is limited.
Carbon-based materials remain the best choice as negative electrodes for lithium batteries because of their excellent electrical conductivity and physicochemical stability. Theoretically, the lithium ion battery has higher graphitization degree and large specific surface area, and is beneficial to realizing the storage and the migration of lithium ions. The existing methods for preparing high-graphitization-degree carbon are divided into two types, one is that abundant pore structures are obtained by polymerizing small-molecule precursors on a template, and then high-temperature graphitization is carried out. Another class is obtained by using high temperature carbonization activation of biomass. Such as SiO at Wuhan university of Engineers2The nano particles are used as a template as a non-metal catalyst, polyaniline grows on the surface of phytic acid, and the porous carbon material with high graphitization degree and large specific surface area is obtained to be used as a lithium ion battery and a sodium ion battery, and the high capacity and the excellent rate capability are obtained (J.Mater.chem.A., 2021,9, 1260-1268). InThe carbon precursor with thermal expansion property used by the institute of chemical and physical university of national academy of sciences expands at low temperature to form a gel structure, and then is further graphitized at high temperature to obtain high-graphitization-degree carbon (CN108178156A) with a developed pore channel structure. The Tianjin technology university obtains a hard carbon negative electrode material by pre-carbonization and carbonization at 1300 ℃ for 2 hours, and then obtains a specific capacity of 350mAh/g (CN113651307A) when the hard carbon negative electrode material is used as a lithium battery negative electrode under the current density of 10 mA/g. The method has the disadvantages of complicated steps, unavoidable template removal, high energy consumption, high safety requirement on equipment and high temperature required by the method generally higher than 1000 ℃. In addition, the high temperature graphitization process can cause shrinkage or collapse of the pore structure.
Therefore, obtaining porous carbon with high graphitization degree by a simple way at a relatively low temperature is a difficult problem to be solved urgently.
Disclosure of Invention
Aiming at the defects that the steps for preparing the carbon-based material are complicated, the pore structure is easy to shrink or collapse when the process temperature is higher than 1000 ℃ and the like in the prior art, the invention aims to provide a method for synthesizing porous carbon with high graphitization degree by a lower-temperature one-step method.
In order to solve the technical problems, the invention adopts a technical scheme that: a preparation method of a high-graphitization-degree carbon-based material for a lithium battery negative electrode comprises the following steps:
step 3, placing the carbon nitride powder obtained in the step 1 in water, stirring to form a suspension, dropwise adding the clear solution obtained in the step 2 into the suspension, stirring for 0.5-1h, performing suction filtration, and drying to obtain porous catalyst/carbon nitride powder;
step 4, crushing the solid asphalt into asphalt powder, and not processing the liquid heavy oil residue precursor;
and 6, placing the mixture obtained in the step 5 in a horizontal tube furnace, slowly heating to 600-900 ℃ under the protection of inert atmosphere, and calcining at constant temperature for 0.5-5h to obtain the high-graphitization-degree carbon-based material.
Further, the slow temperature rise in the step 1 is 1-5 ℃ per minute.
Further, the soluble salt in the step 2 is sulfate or nitrate.
Further, an ammonium molybdate auxiliary agent can also be added in the step 2.
Further, in the step 3, after the drying, an activation treatment step is further included, which specifically includes:
placing the dried product in a vacuum tube furnace device at a speed of 3X 103Pa-5×103Raising the temperature to 800 ℃ at the rate of 10-20 ℃ per minute under the Pa vacuum degree, keeping the temperature constant for 0.5-3h, and reducing the temperature to room temperature to obtain activated catalyst/carbon nitride powder;
and (3) stirring and cleaning the catalyst/carbon nitride powder by using distilled water or 1-2mol/L hydrochloric acid, cleaning to be neutral, and drying for 1-2h at 50-100 ℃ to obtain a porous catalyst/carbon nitride powder product, wherein the powder product after activation treatment has high specific surface area and stable porous structure.
Further, the particle size of the asphalt powder in the step 4 is 100-500 meshes.
Further, the solid-state mixing manner in step 5 may be pulverizer stirring, low-temperature ball milling or manual stirring.
Further, the inert atmosphere in step 6 is nitrogen or argon.
Further, the slow temperature rise in the step 6 is 2-10 ℃ per minute.
Further, in the step 6, after the constant-temperature calcination, a plasma treatment step is further included, which specifically includes:
cooling the product to room temperature and placing the product at 5X 10-3Pa-10×10-3And (3) in a Pa vacuum closed container, keeping the temperature at 30-50 ℃, introducing high-purity argon under the current of 0.1-0.3A to generate plasma, treating the product for 10-30 minutes, washing the treated product with distilled water for multiple times, and drying at 50-100 ℃ to obtain the uniformly dispersed high-graphitization-degree carbon-based material.
The invention has the beneficial effects that:
the invention aims to provide a method for synthesizing a porous carbon-based material with high graphitization degree by a lower-temperature one-step method, the method is simple in preparation steps and high in safety, and the prepared porous carbon-based material with high graphitization degree can be applied to the negative electrode of a lithium battery or other electrochemical energy storage aspects.
The method takes melamine or urea as a raw material, adds soluble salt solution of iron, cobalt and nickel, stirs, filters, dries, and the catalyst/carbon nitride powder prepared by treatment has the characteristics of high specific surface area and stable porous structure; adding asphalt, and stirring and mixing with porous catalyst/carbon nitride powder to obtain a mixture with a compact porous structure, so that a large number of cavities can be provided for lithium storage; the compact mixture is heated and treated by plasma in the inert atmosphere, metal ions on the surface of the mixture material are reduced, loss is reduced, and the uniformly dispersed porous carbon-based material with high graphitization degree has strong conductivity and wear resistance.
Drawings
FIG. 1 is a transmission electron micrograph of the porous carbon obtained in example 1;
FIG. 2 is a transmission electron microscope high resolution image of the porous carbon obtained in example 1;
FIG. 3 is a graph of rate performance of the porous carbon obtained in example 1 at different current densities;
FIG. 4 is a graph showing the cycle characteristics of the porous carbon obtained in example 1 at a current density of 0.5A/g;
fig. 5 is a graph of rate performance of comparative example 1 at different current densities.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Example 1
Putting urea in a porcelain boat, compacting the powder, and sealing with a cover. Placing the mixture in a muffle furnace, raising the temperature to 450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 hours to obtain lamellar carbon nitride light yellow powder. The carbon nitride powder is put into water and stirred to form a suspension. 0.2g of nickel nitrate is dissolved in a proper amount of water and is dropwise added into the carbon nitride suspension. Stirring for 0.5h, filtering, and drying to obtain the catalyst/carbon nitride powder. 1g of asphalt powder and 2g of the catalyst/carbon nitride powder are put into a Jiuyang soybean milk machine to be crushed at high speed and mixed uniformly physically. And (3) placing the mixed material in a horizontal tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere nitrogen, and calcining for 1h at constant temperature.
The transmission electron microscope image of the obtained porous carbon is shown in fig. 1, which is seen to be in a thin layer of porous shape, and through high resolution (fig. 2), it can be seen that there are distinct graphitized stripes at the edge of the carbon layer, which indicates that the obtained carbon has a certain graphitization degree. The conductivity of the resulting porous carbon was 756S/m by the four-probe conductivity test.
FIG. 3 is a graph showing the rate performance of the material as a negative electrode of a lithium battery, wherein 600mAh/g of specific capacity can be obtained at 0.1A/g, and the specific capacity is about 300mAh/g at 2.5A/g.
The capacity is not attenuated after the current density of 0.2A/g is cycled for 400 cycles (figure 4), and the excellent lithium battery negative electrode performance is shown. Compared with comparative example 1, the capacity is improved by about 100mAh/g under the same current density.
Example 2
Putting melamine into a porcelain boat, compacting the powder, and sealing the cover. Placing the mixture in a muffle furnace, raising the temperature to 450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 hours to obtain lamellar carbon nitride light yellow powder. The carbon nitride powder is put into water and stirred to form a suspension. 0.5g of nickel nitrate is dissolved in a proper amount of water and is dropwise added into the carbon nitride suspension. Stirring for 0.5h, filtering, and drying to obtain the catalyst/carbon nitride powder. 2g of vacuum residue and 1g of the catalyst/carbon nitride powder are directly stirred into paste in a porcelain boat. And (3) placing the mixed material in a horizontal tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere nitrogen, and calcining for 1h at constant temperature. The morphology and the negative electrode performance of the obtained material are similar to those of example 1.
Example 3
Putting urea in a porcelain boat, compacting the powder, and sealing with a cover. Placing the mixture in a muffle furnace, raising the temperature to 450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 hours to obtain lamellar carbon nitride light yellow powder. The carbon nitride powder is put into water and stirred to form a suspension. 0.5g of nickel nitrate and 0.1g of ammonium molybdate are dissolved in a proper amount of water together, and the mixture is dripped into the carbon nitride suspension dropwise. Stirring for 0.5h, filtering, and drying to obtain the catalyst/carbon nitride powder. 1g of asphalt powder and 2g of the catalyst/carbon nitride powder are put into a Jiuyang soybean milk machine to be crushed at high speed and mixed uniformly physically. And (3) placing the mixed material in a horizontal tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere nitrogen, and calcining for 1h at constant temperature. The morphology and the negative electrode performance of the obtained material are similar to those of example 1.
Example 4
Putting urea in a porcelain boat, compacting the powder, and sealing with a cover. Placing the mixture in a muffle furnace, raising the temperature to 450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 hours to obtain lamellar carbon nitride light yellow powder. The carbon nitride powder is put into water and stirred to form a suspension. 0.5g of nickel nitrate and 0.1g of ammonium molybdate are dissolved in a proper amount of water together, and the mixture is dripped into the carbon nitride suspension dropwise. Stirring for 0.5h, filtering, and drying to obtain the catalyst/carbon nitride powder. 2g of vacuum residue and 2g of the catalyst/carbon nitride powder are directly stirred into paste in a porcelain boat. And (3) placing the mixed material in a horizontal tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere nitrogen, and calcining for 1h at constant temperature. The morphology and the negative electrode performance of the obtained material are similar to those of example 1.
Comparative example 1
Putting urea in a porcelain boat, compacting the powder, and sealing with a cover. Placing the mixture in a muffle furnace, raising the temperature to 450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 hours to obtain lamellar carbon nitride light yellow powder. The carbon nitride powder is put into water and stirred to form a suspension. Directly placing 1g of asphalt powder and 2g of carbon nitride powder in a Jiuyang soybean milk machine for high-speed crushing, and physically and uniformly mixing. And (3) placing the mixed material in a horizontal tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of inert atmosphere nitrogen, and calcining for 1h at constant temperature. The resulting material morphology was similar to example 1. The resulting comparative material was used as a negative electrode for a lithium battery and the rate curves at different current densities are shown in fig. 5.
Example 5
In step 3, after drying, the method further comprises an activation treatment step, and specifically comprises the following steps:
placing the dried product in a vacuum tube furnace device at a speed of 3X 103Under the Pa vacuum degree, raising the temperature to 600 ℃ at the rate of 150 ℃ per minute, keeping the temperature constant for 2h, and reducing the temperature to room temperature to obtain activated catalyst/carbon nitride powder;
and (3) stirring and cleaning the catalyst/carbon nitride powder by using distilled water, cleaning to be neutral, drying for 1.5h at 100 ℃ to obtain a porous catalyst/carbon nitride powder product, wherein the powder product after activation treatment has high specific surface area and stable porous structure.
In this example, the catalyst/carbon nitride powder obtained by the treatment has the characteristics of high specific surface area and stable porous structure.
Example 6
In step 6, after the constant temperature calcination, a plasma treatment step is further included, which specifically includes: cooling the product to room temperature and placing the product at 5X 10-3And (3) in a Pa vacuum closed container, keeping the temperature at 30 ℃, introducing high-purity argon under the current of 0.1A to generate plasma, treating the product for 30 minutes, washing the treated product with distilled water for multiple times, and drying at 60 ℃ to obtain the uniformly dispersed high-graphitization-degree carbon-based material.
In the embodiment, the plasma treatment can reduce metal ions on the surface of the mixture material, so that loss is reduced, and the uniformly dispersed high-graphitization-degree porous carbon-based material has high conductivity and wear resistance.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-graphitization-degree carbon-based material for a lithium battery negative electrode is characterized by comprising the following steps of: the method comprises the following steps:
step 1, placing melamine or urea in a porcelain boat, compacting the powder, covering and sealing the porcelain boat, placing the porcelain boat in a muffle furnace, slowly heating to 400-600 ℃, and preserving heat for 1-5 hours to obtain lamellar light yellow carbon nitride powder;
step 2, dissolving soluble salts of iron, cobalt and nickel in a proper amount of water to obtain a clear solution;
step 3, placing the carbon nitride powder obtained in the step 1 in water, stirring to form a suspension, dropwise adding the clear solution obtained in the step 2 into the suspension, stirring for 0.5-1h, performing suction filtration, and drying to obtain porous catalyst/carbon nitride powder;
step 4, crushing the solid asphalt into asphalt powder, and not processing the liquid heavy oil residue precursor;
step 5, directly mixing the catalyst/carbon nitride powder and the asphalt powder in a solid state according to the proportion of 1: 0.1-10; or directly adding the heavy oil residue precursor with flow state into carbon nitride powder, and stirring into paste;
and 6, placing the mixture obtained in the step 5 in a horizontal tube furnace, slowly heating to 600-900 ℃ under the protection of inert atmosphere, and calcining at constant temperature for 0.5-5h to obtain the high-graphitization-degree carbon-based material.
2. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: in the step 1, the slow temperature rise is 1-5 ℃ per minute.
3. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: in the step 2, the soluble salt is sulfate or nitrate.
4. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: an ammonium molybdate auxiliary agent can also be added in the step 2.
5. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: in the step 3, after the drying, an activation treatment step is further included, which specifically includes:
placing the dried product in a vacuum tube furnace device at a speed of 3X 103Pa-5×103Raising the temperature to 800 ℃ at the rate of 10-20 ℃ per minute under the Pa vacuum degree, keeping the temperature constant for 0.5-3h, and reducing the temperature to room temperature to obtain activated catalyst/carbon nitride powder;
and stirring and cleaning the catalyst/carbon nitride powder by using distilled water or 1-2mol/L hydrochloric acid, cleaning to be neutral, and drying at 50-100 ℃ for 1-2h to obtain a porous catalyst/carbon nitride powder product.
6. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: the particle size of the asphalt powder in the step 4 is 100-500 meshes.
7. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: the solid state mixing mode in the step 5 can be stirring by a pulverizer, low-temperature ball milling or manual stirring.
8. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: and in the step 6, the inert atmosphere is nitrogen or argon.
9. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: in the step 6, the slow temperature rise is 2-10 ℃ per minute.
10. The method for preparing the carbon-based material with high graphitization degree for the negative electrode of the lithium battery according to the claim 1, characterized by comprising the following steps: in the step 6, after the constant temperature calcination, a plasma treatment step is further included, which specifically includes:
cooling the product to room temperature and placing the product at 5X 10-3Pa-10×10-3And (3) in a Pa vacuum closed container, keeping the temperature at 30-50 ℃, introducing high-purity argon under the current of 0.1-0.3A to generate plasma, treating the product for 10-30 minutes, washing the treated product with distilled water for multiple times, and drying at 50-100 ℃ to obtain the uniformly dispersed high-graphitization-degree carbon-based material.
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