CN108123110B - Preparation method and application of nitrogen-containing large-pore-volume porous carbon material - Google Patents

Preparation method and application of nitrogen-containing large-pore-volume porous carbon material Download PDF

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CN108123110B
CN108123110B CN201611067619.XA CN201611067619A CN108123110B CN 108123110 B CN108123110 B CN 108123110B CN 201611067619 A CN201611067619 A CN 201611067619A CN 108123110 B CN108123110 B CN 108123110B
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sulfur
porous carbon
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陈剑
孙春水
郭德才
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a preparation method and application of a nitrogen-containing large-pore-volume porous carbon material, and belongs to the technical field of preparation of heteroatom-modified porous carbon materials in functional materials and preparation of lithium-sulfur battery cathode materials. The invention particularly relates to a method for preparing a nitrogen-containing large-pore-volume porous carbon material and a high-sulfur-content sulfur-carbon composite material anode by using biomass gel as a carbon source and adopting an ice and silicon dioxide double-template method through high-temperature pyrolysis. The porous carbon prepared by the invention has nitrogen-oxygen modified surface chemical property and large mesopore volume; the sulfur content of the prepared carbon-sulfur anode material is up to 80 percent by mass by taking the carbon-sulfur anode material as a carrier. The prepared carbon-sulfur composite positive electrode material is used for the lithium-sulfur battery and has better electrochemical performance.

Description

Preparation method and application of nitrogen-containing large-pore-volume porous carbon material
Technical Field
The invention belongs to the technical field of preparation of heteroatom modified porous carbon materials in functional materials and preparation of lithium-sulfur battery anode materials, and particularly relates to a preparation method and application of a nitrogen-containing large-pore-volume porous carbon material.
Background
In today's society, battery devices have become an indispensable and important role in daily life. Under the push of the rapid development of portable electronic devices and electric vehicle technologies, battery technologies have also been rapidly developed. Among a plurality of battery systems, the lithium-sulfur battery has higher theoretical specific capacity (1675mAh/g) and theoretical energy density (2600Wh/kg), and is likely to meet the application requirements of new battery energy storage systems (such as portable electronic equipment, electric vehicles and electrochemical energy storage stations) in the future, and the lithium-sulfur battery has abundant, cheap and environment-friendly raw material reserves, so that the lithium-sulfur battery is widely concerned and researched.
The porous carbon material has developed specific surface area, larger pore volume and good electronic conductivity, not only serves as an electronic conductor in the positive electrode material of the lithium-sulfur battery, but also can relieve polysulfide from diffusing to the negative electrode through the adsorption effect of pores, and can effectively maintain the battery capacity.
The biomass is a renewable carbon precursor with wide source and low price, and has the characteristics of various varieties, renewability and the like. The biomass glue is a macromolecular protein prepared by taking animal skin, bones, tendons or phosphorus as raw materials, is a common natural biological macromolecular material, and has the characteristics of containing various oxygen-containing and nitrogen-containing functional groups and the like. When the biomass glue is used as a precursor to prepare the porous carbon, the pore structure of the carbon can be regulated and controlled by using a hard template as a template. However, the preparation of the porous carbon with the ultra-large pore volume and the rich macroporous structure is difficult to realize by a single hard template, and further the preparation of the carbon-sulfur composite material with high sulfur content is difficult to realize.
Disclosure of Invention
In order to solve the problems, the biomass glue is used as a precursor, silicon oxide is used as a hard template, and a method of freezing in-situ generation of an ice soft template is adopted, so that the prepared carbon material has a large specific surface and a large pore volume, can provide an effective space in a lithium-sulfur battery positive electrode material to prepare a composite material with high sulfur content, and provides a space for volume expansion of sulfur in the charging and discharging processes.
The invention aims to provide a method for preparing a nitrogen-containing large-pore-volume porous carbon material and a lithium-sulfur battery positive electrode material.
The invention aims to provide a preparation method of a nitrogen-containing large-pore-volume porous carbon material, which comprises the following steps:
(1) the preparation process of the biomass glue-SiO 2 sol comprises the following steps: uniformly mixing the aqueous solution of the biomass gum and the silicon dioxide solution according to a certain mass percentage, heating in a water bath, and magnetically stirring to obtain a sol system.
(2) The preparation process of the ice template comprises the following steps: pre-freezing the uniformly mixed sol system to obtain a double-template system; followed by lyophilization.
(3) And (3) carbonization: putting the dried precursor into a tubular furnace, and carrying out pyrolysis carbonization in an argon atmosphere to obtain a carbon material;
(4) and (3) silicon oxide removal: and (3) placing the obtained silicon oxycarbide composite material in an alkali solution, soaking to remove silicon oxide, and then washing with deionized water to be neutral.
(5) Drying and post-treatment: and (4) drying the material obtained in the step 4) by air blowing, and then grinding the dried material to obtain the nitrogen-containing large-pore-volume porous carbon material.
In the step (1), biomass glue is used as a raw material, and the nitrogen-containing macroporous porous carbon is prepared by using an ice and silicon dioxide double-template method. The biomass gum is gelatin, carrageenan or pectin and a mixture thereof, the particle size of silicon dioxide in the silicon dioxide solution is 18-100 nm, and the biomass gum concentration is 1-20 wt%, preferably 2-10 wt%; the mass ratio of the silicon dioxide to the biomass is 0-10, preferably 0-5, the water bath temperature is 30-100 ℃, and preferably 50-70 ℃; the water bath time is 12-48 h, preferably 24-36 h.
In the step (2), the temperature is-10 ℃ to-40 ℃ when the ice template is prepared, the time is 2-5 hours, the ice template is removed in a freeze drying mode, the drying temperature is-20 ℃ to-50 ℃, and the time is 24-48 hours.
In the step (3), the carbonization temperature is 500-1400 ℃, preferably 700-900 ℃; the carbonization time is 0.5-48 h, preferably 2-6 h.
In the step (4), the alkali can be sodium hydroxide or potassium hydroxide or a mixture of the sodium hydroxide and the potassium hydroxide, and the concentration of the alkali liquor is 2-15 wt%, preferably 4-10 wt%; the alkali liquor solvent is a water/ethanol mixed solution, and the ethanol accounts for 10-70 wt%, preferably 30-50 wt%; the temperature for removing silicon oxide is 50-90 ℃, preferably 60-80 ℃; the time for removing the silicon oxide is 5 to 36 hours, preferably 12 to 24 hours. The vacuum drying temperature is 50-80 ℃.
The application of the nitrogen-containing macroporous porous carbon material in preparing the lithium-sulfur battery cathode material comprises the following specific steps:
(1) the preparation process of the sulfur-carbon composite material comprises the following steps: and uniformly mixing the prepared carbon material with elemental sulfur, placing the mixture in a tubular furnace, and carrying out heat treatment in an argon atmosphere to obtain the sulfur-carbon composite material.
(2) The preparation process of the lithium-sulfur battery positive electrode comprises the following steps: and mixing the obtained sulfur-carbon composite material with a binder and a conductive agent according to a certain proportion, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required lithium-sulfur battery cathode material.
In the step (1), the temperature of the first stage of heat treatment is 150 ℃, the treatment time is 6-24 hours, preferably 10-20 hours, the temperature of the second stage is 300 ℃, and the treatment time is 0.5-5 hours, preferably 2-4 hours; the sulfur content of the prepared sulfur-carbon composite material is 50-90%, preferably 60-80%.
The mass ratio of the sulfur-carbon composite material, the binder and the conductive agent in the step (2) is 8/1/1 or 7/2/1, and the binder is: PVDF (polyvinylidene fluoride), the conductive agent being: AB (acetylene black) or VGCF (carbon fiber).
Compared with the prior art and the material, the invention has the following advantages.
1. The raw material biomass glue is a common natural biological high polymer material, and has the characteristics of wide source, various oxygen-containing and nitrogen-containing functional groups and the like. Removing the ice template by freeze drying technology to obtain a pore channel structure after ice sublimation, and removing silicon oxide in the carbon-silicon oxide compound by alkali washing to realize ice and SiO2And the double-template effect is realized, so that the nitrogen-containing porous carbon material with large pore volume and high specific surface area is obtained.
2. By using the method, the pore structure and the morphology of the carbon material can be effectively regulated and controlled by regulating the content of silicon oxide in the biomass glue system and the solid content of the sol system. Because the biomass glue has rich nitrogen-containing functional groups, the porous carbon material modified by nitrogen atoms can be obtained, and the synchronous regulation and control of the surface chemical properties of the carbon material are realized.
Drawings
FIG. 1 is an SEM image of the gelatin carbon material prepared by the present invention.
FIG. 2 is a graph showing the nitrogen adsorption profile of the prepared gelatin carbon material.
FIG. 3 is a first charge-discharge curve diagram of the nano sulfur-carbon composite anode material prepared by the invention.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Gelatin (10 wt% solution) was mixed with an equal amount of SiO2(40 wt% solution, particle size 18nm) and reacted in a water bath at 70 ℃ for 12 h. The resulting solution was frozen at-40 ℃ and then vacuum freeze-dried until complete drying. And (3) placing the dried block material in a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and maintaining for 48 hours. And taking out after the temperature is reduced to room temperature, placing the mixture into 10 wt% NaOH solution, removing silicon for 12 hours at 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture. The dried carbon material was ground into a powder. The obtained powder material is characterized by SEM as shown in figure 1 and is in a porous fluffy state, and the nitrogen adsorption and desorption curve obtained by BET characterization is shown in figure 2 and has higher specific surface area and pore volume. Uniformly mixing the ground carbon and elemental sulfur according to the mass ratio of 1/4 (the sulfur content is about 80%), processing for 12 hours at 150 ℃ in a tubular furnace under the argon atmosphere, and then heating to 300 ℃ for 2 hours to obtain the sulfur-carbon composite material. And mixing the sulfur-carbon composite material with a binder PVDF and a conductive agent AB according to the mass ratio of 7/2/1, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required lithium-sulfur battery cathode material. The charge-discharge curve is shown in figure 3, and the charge-discharge specific capacity is higher.
Example 2
Mixing pectin (1 wt% solution) with 5 times of SiO2(40 wt% solution, particle size 50nm) and reacted in a water bath at 30 ℃ for 24 h. The resulting solution was frozen at-10 ℃ and then vacuum freeze-dried until complete drying. And (3) placing the dried block material in a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, and maintaining for 2 h. And taking out after the temperature is reduced to room temperature, placing the mixture into 15 wt% NaOH solution, removing silicon for 24 hours at 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture. The dried carbon material was ground into a powder. The SEM characteristic is similar to that of figure 1, the sample is porous and fluffy, the BET characteristic shows that the sample is in a porous state, the pore volume is large, and the value is related to the template content. Mixing the ground carbon with elemental sulfur1/1 (the sulfur content is about 50 percent), treating for 24 hours at 150 ℃ in a tube furnace under the argon atmosphere, and then heating to 300 ℃ for 0.5 hour to obtain the sulfur-carbon composite material. And mixing the sulfur-carbon composite material with PVDF as a binder and VGCF as a conductive agent according to the mass ratio of 8/1/1, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required positive electrode material of the lithium-sulfur battery. The charge-discharge curve is close to that of FIG. 3, and the values are different.
Example 3
Mixing carrageenan (20 wt% solution) and 10 times of SiO2(40 wt% solution, particle size 100nm) and reacted in an oil bath at 100 ℃ for 48 h. The resulting solution was frozen at-20 ℃ and then vacuum freeze-dried until complete drying. And (3) placing the dried block material in a tube furnace, heating to 1400 ℃ at the speed of 5 ℃/min under the argon atmosphere, and maintaining for 0.5 h. And taking out after the temperature is reduced to room temperature, placing the mixture into 10 wt% NaOH solution, removing silicon for 24 hours at 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture. The SEM characteristic is similar to that of figure 1, the sample is porous and fluffy, the BET characteristic shows that the sample is in a porous state, the pore volume is large, and the value is related to the template content. The dried carbon material was ground into a powder. Uniformly mixing the ground carbon and elemental sulfur according to the mass ratio of 1/9 (the sulfur content is about 90%), processing for 6 hours at 150 ℃ in a tubular furnace under the argon atmosphere, and then heating to 300 ℃ for 5 hours to obtain the sulfur-carbon composite material. And mixing the sulfur-carbon composite material with a binder PVDF and a conductive agent AB according to the mass ratio of 7/2/1, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required lithium-sulfur battery cathode material. The charge-discharge curve is close to that of FIG. 3, and the values are different.
Example 4
Mixing gelatin (10 wt% solution) with no SiO2And reacting for 24 hours in a water bath at 70 ℃. The resulting solution was frozen at-40 ℃ and then vacuum freeze-dried until complete drying. And (3) placing the dried block material in a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, and maintaining for 4 h. Taking out after the temperature is reduced to room temperature, placing the mixture in 2 wt% NaOH solution to remove silicon for 36h at 50 ℃, then washing the mixture to be neutral by deionized water, andand (5) drying. The SEM characteristic is similar to that of figure 1, the sample is porous and fluffy, the BET characteristic shows that the sample is in a porous state, the pore volume is large, and the value is related to the template content. The dried carbon material was ground into a powder. Uniformly mixing the ground carbon and elemental sulfur according to the mass ratio of 1/4 (the sulfur content is about 80%), processing for 12 hours at 150 ℃ in a tubular furnace under the argon atmosphere, and then heating to 300 ℃ for 2 hours to obtain the sulfur-carbon composite material. And mixing the sulfur-carbon composite material with a binder PVDF and a conductive agent AB according to the mass ratio of 8/1/1, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required lithium-sulfur battery cathode material. The charge-discharge curve is close to that of FIG. 3, and the values are different.
Example 5
Mixing gelatin (8 wt% solution) with 1.5 times of SiO2(40 wt% solution) and reacted in a water bath at 70 ℃ for 12 h. The resulting solution was frozen at-40 ℃ and then vacuum freeze-dried until complete drying. And (3) placing the dried block material in a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, and maintaining for 2 h. And taking out after the temperature is reduced to room temperature, placing the mixture into 10 wt% NaOH solution, removing silicon for 5 hours at 90 ℃, washing the mixture to be neutral by deionized water, and drying the mixture. The SEM characteristic is similar to that of figure 1, the sample is porous and fluffy, the BET characteristic shows that the sample is in a porous state, the pore volume is large, and the value is related to the template content. The dried carbon material was ground into a powder. Uniformly mixing the ground carbon and elemental sulfur according to the mass ratio of 1/4 (the sulfur content is about 80%), processing for 12 hours at 150 ℃ in a tubular furnace under the argon atmosphere, and then heating to 300 ℃ for 2 hours to obtain the sulfur-carbon composite material. And mixing the sulfur-carbon composite material with PVDF as a binder and VGCF as a conductive agent according to the mass ratio of 8/1/1, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required positive electrode material of the lithium-sulfur battery. The charge-discharge curve is close to that of FIG. 3, and the values are different.

Claims (12)

1. A preparation method of a nitrogen-containing macroporous porous carbon material is characterized by comprising the following steps:
(1) biomass glue-SiO2The sol preparation process comprises the following steps: will growUniformly mixing an aqueous solution of a substance glue and a silicon dioxide solution according to a certain mass percentage, heating by using water or an oil bath, and magnetically stirring to obtain a sol system;
(2) the preparation process of the ice template comprises the following steps: pre-freezing the uniformly mixed sol system to obtain a double-template system; then freeze-drying is carried out;
(3) and (3) carbonization: putting the dried precursor into a tubular furnace, and carrying out pyrolysis carbonization in an argon atmosphere to obtain a carbon material;
(4) and (3) silicon oxide removal: placing the obtained silicon oxycarbide composite material in an alkali solution, soaking to remove silicon oxide, and then washing with deionized water to be neutral;
(5) drying and post-treatment: and (4) drying the material obtained in the step 4) by air blowing, and then grinding the dried material to obtain the nitrogen-containing large-pore-volume porous carbon material.
2. The method for preparing a nitrogen-containing large-pore-volume porous carbon material according to claim 1, wherein the biomass gum is gelatin, carrageenan, pectin or a mixture of any two of the gelatin, and the particle size of silica in the silica solution is 18-100 nm.
3. The method for preparing a nitrogen-containing macroporous porous carbon material according to claim 1, wherein in the step 1), the concentration of the biomass glue solution is 1-20 wt%; the mass ratio of the silicon dioxide to the biomass glue is 0-10, and the temperature of water or oil bath is 30-100 ℃; the water bath time is 12-48 h.
4. The method for preparing the nitrogen-containing macroporous porous carbon material according to claim 1, wherein in the step 1), the concentration of the biomass glue solution is 2 wt% -10 wt%, the mass ratio of the silicon dioxide to the biomass glue is 0-5, the water bath temperature is 50-70 ℃, and the water bath time is 24-36 h.
5. The method for producing a nitrogen-containing large pore volume porous carbon material according to claim 1, wherein in the step 3), the carbonization temperature is 500 ℃ to 1400 ℃; the carbonization time is 0.5-48 h.
6. The method for producing a nitrogen-containing large pore volume porous carbon material according to claim 1, wherein in the step 3), the temperature of carbonization is 700 ℃ to 900 ℃; the carbonization time is 2-6 h.
7. The method for preparing a porous carbon material containing nitrogen with a large pore volume according to claim 1, wherein in the step 4), the alkali is sodium hydroxide, potassium hydroxide or a mixture of the sodium hydroxide and the potassium hydroxide, and the concentration of the alkali solution is 2-15 wt%; the alkali liquor solvent is a mixed solution of water and ethanol, and the ethanol accounts for 10-70 wt%; the temperature for removing silicon oxide is 50-90 ℃; the time for removing the silicon oxide is 5 to 36 hours.
8. The method for preparing a porous carbon material containing nitrogen and having a large pore volume according to claim 6, wherein in the step 4), the concentration of the alkali solution is 4 to 10 wt%; the alkali liquor solvent is a mixed solution of water and ethanol, and the ethanol accounts for 30-50 wt% of the mass ratio; the temperature for removing silicon oxide is 60-80 ℃; the time for removing the silicon oxide is 12-24 h.
9. The application of the nitrogen-containing large pore volume porous carbon material prepared by the preparation method of the nitrogen-containing large pore volume porous carbon material according to claim 1 is characterized in that the nitrogen-containing large pore volume porous carbon material is used for preparing a lithium-sulfur battery anode material, a lithium ion battery cathode material and a supercapacitor, the prepared porous carbon is used for carrying other electrochemical active substances to prepare a carbon-based composite electrode material, and the specific steps for preparing the lithium-sulfur battery anode material are as follows:
(1) preparing a sulfur-carbon composite material: uniformly mixing the prepared nitrogen-containing macroporous porous carbon material with elemental sulfur, placing the mixture in a tubular furnace, and carrying out heat treatment in an argon atmosphere to obtain a sulfur-carbon composite material;
(2) preparation of the lithium-sulfur battery positive electrode: and mixing the obtained sulfur-carbon composite material with a binder and a conductive agent according to a certain proportion, preparing slurry by taking nitrogen-methyl pyrrolidone as a solvent, uniformly coating the slurry on a carbon-coated aluminum foil, and drying to obtain the required lithium-sulfur battery cathode material.
10. The use of the nitrogen-containing macroporous porous carbon material as claimed in claim 9, wherein in the step (1), the heat treatment is specifically: the temperature of the first stage is 150 ℃, the treatment time is 6-24 h, the temperature of the second stage is 300 ℃, and the treatment time is 0.5-5 h; the sulfur content of the prepared sulfur-carbon composite material is 50-90%.
11. The application of the nitrogen-containing macroporous porous carbon material as claimed in claim 9, wherein in the step (1), the temperature of the first stage of the heat treatment is 150 ℃, the treatment time is 10-20 hours, the temperature of the second stage is 300 ℃, and the treatment time is 2-4 hours; the sulfur content of the prepared sulfur-carbon composite material is 60-80%.
12. The use of the nitrogen-containing macroporous porous carbon material as claimed in claim 9, wherein the mass ratio of the sulfur-carbon composite material, the binder and the conductive agent in step (2) is 8/1/1 or 7/2/1, and the binder is: polyvinylidene fluoride, the conductive agent being: acetylene black or carbon fibers.
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