CN110921645B - Dual-template multi-stage porous carbon-based material and preparation method and application thereof - Google Patents
Dual-template multi-stage porous carbon-based material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a double-template multi-stage porous carbon-based material, which comprises the following steps: generating a mesoporous silica layer on the surface of bacteria by taking the bacteria as a template to obtain a mesoporous silica layer/bacteria composite template; synthesizing a carbon source in the pore channel of the mesoporous silica layer, carbonizing in a protective atmosphere, and removing the mesoporous silica layer to obtain the dual-template multi-stage porous carbon-based material; wherein the carbon source is selected from one of polyaniline, polypyrrole, dopamine, phenolic resin and sucrose. The invention also provides the double-template multistage porous carbon-based material prepared by the method and application thereof. The template of the multi-stage porous carbon-based material is derived from bacteria widely existing in life, is easy to prepare in large quantities and is easy to implement in industrial production; the selected materials are non-toxic and harmless to the environment and almost have no pollution; the preparation method solves the problem that the growth of the surface appearance of the material is difficult to control in the prior art.
Description
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to a double-template multi-stage porous carbon-based material and a preparation method and application thereof.
Background
Sulfur is a non-metallic element widely present in nature, and elemental sulfur and sulfur compounds are widely present in various minerals and the atmosphere. The elemental sulfur has the characteristics of small relative molecular mass, more transferred electron numbers by reaction with lithium and the like, the theoretical specific capacity of the sulfur lithium battery taking the elemental sulfur as the anode material is up to 1675mAh/g, the theoretical energy density is up to 2600Wh/kg, and the theoretical specific capacity is obviously higher than that of the current commercial lithium ion battery. In addition, the sulfur has low price, environmental protection and easy obtainment, and has wide application prospect in the aspects of energy storage of chemical power sources, environmental pollution improvement of the existing batteries and the like. Elemental sulfur is a typical electron ion insulator at room temperature (5 x 10)-30S/cm), so that the elemental sulfur has high activation difficulty and low utilization rate of active materials when used as a positive active material. In addition, a large amount of lithium polysulfide generated during discharge can be dissolved in electrolyte, so that the loss of positive active substances is caused, the cycle life is reduced, and the volume expansion effect is up to 80% during the material form conversion in the charge-discharge process of elemental sulfur, so that the electrode is causedCrushing and destroying; furthermore, the final discharge product of lithium-sulfur batteries, Li2S2/Li2S can deposit on the pole piece to form an insulated lithium polysulfide film, and the redox reaction kinetics of the battery material is slowed down. The above problems result in low utilization of active materials and rapid capacity fade of lithium-sulfur batteries. Therefore, it is very important to research how to improve the sulfur utilization rate.
The multi-stage porous carbon-based material has the advantages of stable physical and chemical properties, high specific surface area, high pore capacity, high conductivity and the like, and as a storage matrix material of elemental sulfur, the rich pore channel structure of the multi-stage porous carbon-based material can store a large amount of elemental sulfur, improve the conductivity of an electrode and inhibit the diffusion of lithium polysulfide in the charging and discharging processes, so that the sulfur-carbon composite positive electrode material is widely researched and applied to lithium-sulfur batteries.
The carbon element is widely distributed in organisms in the form of compounds, the inner membrane structure and the framework structure of the organisms are numerous, such as an intracellular protein framework, an intracellular organelle membrane and the like, and organic matters in the organisms generally contain phosphorus and nitrogen, and the uniform porous phosphorus-nitrogen doped carbon material can be directly obtained after the carbonization treatment of the phosphorus and nitrogen element. The bacteria have the characteristics of various shapes, diversified constituent elements and the like, and can be used as a biomass template to construct a carbon-based material with an excellent structure.
Disclosure of Invention
The invention aims to provide a double-template multilevel porous carbon-based material and a preparation method thereof, wherein the template of the multilevel porous carbon-based material is derived from bacteria widely existing in life, is easy to prepare in large quantities and is easy to implement in industrial production; and the selected materials are non-toxic and harmless to the environment and almost have no pollution. The preparation method solves the problem that the growth of the surface appearance of the material is difficult to control in the prior art.
In order to solve the technical problem, the invention provides a preparation method of a double-template multi-stage porous carbon-based material, which comprises the following steps:
generating a mesoporous silica layer on the surface of bacteria by taking the bacteria as a template to obtain a mesoporous silica layer/bacteria composite template; and
synthesizing a carbon source in the pore channel of the mesoporous silica layer, then carbonizing in a protective atmosphere, and removing the mesoporous silica layer to obtain the dual-template multi-stage porous carbon-based material;
wherein the carbon source is selected from one of polyaniline, polypyrrole, dopamine, phenolic resin and sucrose.
In the present invention, the carbon source is preferably a nitrogen-doped carbon source, such as polyaniline, polypyrrole, dopamine, and the like. The nitrogen doping can improve the adsorption effect of the carbon-based material on polysulfide and simultaneously improve the polarity and the conductivity of the carbon-based material.
According to the invention, bacteria and a mesoporous silica layer formed on the surface of the bacteria are used as double templates, a carbon source is synthesized in a pore channel of mesoporous silica, and after the mesoporous silica template is carbonized and removed, the porous carbon-based material with a multilevel structure is obtained.
Further, the bacteria are selected from at least one of cocci, bacilli and spirochetes (including vibrio, spirochete, helicobacter). Preferably, the bacterium is escherichia coli.
Further, the mesoporous silica layer/bacterial composite template is obtained by mixing and reacting bacterial liquid, tetraethyl orthosilicate and a template agent. Wherein the template agent is preferably Cetyl Trimethyl Ammonium Bromide (CTAB).
Further, OD of the bacterial liquid600nmThe value is 80 to 120, for example, 80,100,120, etc.
Further, the nitrogen-doped carbon source is polyaniline, and the synthesis method comprises the following steps: mixing the mesoporous silica layer/bacteria composite template with aniline, and reacting in the presence of an oxidant to synthesize polyaniline in the pore canal of the mesoporous silica layer. The oxidant is preferably ammonium persulfate-sulfuric acid solution.
Further, the weight ratio of the bacteria to the tetraethyl orthosilicate to the aniline is 0.5:2.5: 0.5-2. Wherein the weight of bacteria is dry weight.
Further, the carbonization conditions are as follows: carbonizing at 600-900 ℃, wherein the carbonizing time is 3-6 hours, the heating rate is 2-10 ℃/min, and preferably 5 ℃/min.
Further, the protective atmosphere is selected from at least one of nitrogen, helium and argon. Preferably nitrogen or argon.
The method for removing the mesoporous silica template comprises the following steps: and soaking the carbonized material in hot sodium hydroxide solution or hydrofluoric acid.
The invention also provides a double-template multi-stage porous carbon-based material prepared by the method.
The invention also provides application of the double-template multistage porous carbon-based material in preparation of an electrode material of a lithium-sulfur battery.
The invention has the beneficial effects that:
1. the invention takes the bacteria widely existing in life as a template, is easy to prepare in large quantity and implement in industrial production, and the selected materials are nontoxic and harmless to the environment and almost pollution-free; and the method solves the problem that the surface appearance growth of the material cannot be controlled in the prior art.
2. The multi-stage porous carbon-based material prepared by the invention can store elemental sulfur with the mass more than 2 times that of the carbon material, and when the multi-stage porous carbon-based material is applied as a sulfur storage matrix material, the multi-stage porous carbon-based material shows good energy storage and cycle performance and coulombic efficiency.
Drawings
Fig. 1 is an SEM image of the multi-stage porous carbon-based material prepared in example 1;
FIG. 2 is a TEM image of the multi-stage porous carbon-based material prepared in example 1;
fig. 3 is a BET diagram of the multi-stage porous carbon-based material prepared in example 1;
fig. 4 is a pore size distribution diagram of the multi-stage porous carbon-based material prepared in example 1;
fig. 5 is a charge-discharge graph of the multi-stage porous carbon-based material sulfur storage composite electrode prepared in example 1 in a lithium sulfur battery;
fig. 6 is a graph of rate performance of the multi-stage porous carbon-based material sulfur storage composite electrode prepared in example 1 in a lithium sulfur battery;
fig. 7 is a charge-discharge image of the multi-stage porous carbon-based material sulfur storage composite electrode prepared in example 2 in a lithium sulfur battery;
fig. 8 is a graph of rate performance of the multi-stage porous carbon-based material sulfur storage composite electrode prepared in example 2 in a lithium sulfur battery.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
In the following examples, the room temperature is 25 ℃. The escherichia coli liquid (the absorbance is 100OD in a 600nm photometric instrument) is cultured by life science college of Suzhou university medical department, and is centrifugally collected and inactivated by glutaraldehyde to obtain the solidified escherichia coli liquid.
Example 1
1. Preparation of double-template multi-stage porous carbon-based material
30mL of 100OD solidified escherichia coli liquid is added into 80mL of deionized water, and stirred to form uniform bacterial suspension, then 0.5g of hexadecyl trimethyl ammonium bromide and 0.8mL of saturated ammonia water are added, and stirring is carried out for 10min at the rotating speed of 170rpm under the condition of 30 ℃. Then n-hexane was added and stirring was continued for 10min, and then 2.5mL of tetraethyl orthosilicate was added and stirred for 12 hours.
Washing a mesoporous pore channel with ethanol for 3 hours after centrifugal collection, then centrifugally collecting, spreading 0.5g of washed sample at the bottom of a 25mL beaker, dropwise adding 1mL of ethanol and uniformly stirring, then adding 1mL of aniline, performing ultrasonic treatment for 5min, dropwise adding 9mL of sulfuric acid solution of ammonium persulfate, continuously stirring to uniformly react, then raising the temperature to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon gas for carbonization for 3 hours, cooling to room temperature after carbonization, soaking in 20% hydrofluoric acid solution for 12 hours, centrifugally drying, and grinding to obtain the capsule-shaped multi-stage porous carbon-based material.
Fig. 1-2 are SEM and TEM images of the multi-stage porous carbon-based material prepared in example 1, respectively. As can be seen from the figure, the prepared multi-stage porous carbon-based material has a uniform-sized capsule-like structure with a size of several micrometers.
FIGS. 3-4 are BET graphs of the multi-stage porous carbon-based material, from which it can be concluded that the multi-stage porous carbon-based material has an average pore diameter of 3.3nm and an average specific surface area of 650cm2/g。
2. Electrochemical performance test
The multi-stage porous carbon-based material prepared in example 1 is weighed according to the mass ratio of 8:1: conductive carbon black (Super-P) acrylonitrile multipolymer (LA), grinding uniformly to make electrode, using metal lithium as battery negative electrode and electrolyte of 0.1M LiNO3Per DME/DOL (1:1, vol., LiNO)3Dimethyl ether (DME) and 1, 3-Dioxolane (DOL) in a volume ratio of 1:1 are used as solvents to prepare 0.1M solution), and a polypropylene microporous film is used as a diaphragm to assemble the simulated lithium-sulfur battery. The simulated lithium sulfur cell was subjected to a cycling test on a blue test instrument at a current density of 0.2C and a voltage interval of 1.7-2.8V, and the results are shown in fig. 5-6.
As can be seen from FIGS. 5-6, the capacity of the first cycle is up to 1200mAh/g at 0.2C, and after 100 cycles of stable circulation, the capacity of 970mAh/g is still maintained. The multiplying power can be circulated to 1C, and when the multiplying power is changed to 0.1C again, the capacity is still kept above 1000mAh/g, and the excellent electrochemical performance is shown.
Example 2
Example 2 differs from example 1 only in that: the amount of aniline added was 0.5 mL.
The multi-stage porous carbon-based material prepared in this example was further prepared into an electrode according to the method of example 1, and assembled into a lithium sulfur battery, which was subjected to a cycling test on a blue test instrument at a current density of 0.2C and a voltage interval of 1.7 to 2.8V, and the results thereof were shown in fig. 7 to 8.
As can be seen from fig. 7 to 8, the lithium-sulfur battery of the present example has a capacity of 1000mAh/g at 0.2C for the first cycle, and maintains a capacity of 700mAh/g after 100 cycles of stable cycling, showing excellent electrochemical performance.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a double-template multi-stage porous carbon-based material is characterized by comprising the following steps:
generating a mesoporous silica layer on the surface of bacteria by taking the bacteria as a template to obtain a mesoporous silica layer/bacteria composite template; and
synthesizing a carbon source in the pore channel of the mesoporous silica layer, then carbonizing in a protective atmosphere, and removing the mesoporous silica layer to obtain the dual-template multi-stage porous carbon-based material;
wherein the carbon source is selected from one of polyaniline, polypyrrole, dopamine, phenolic resin and sucrose.
2. The method for preparing the dual-template multi-stage porous carbon-based material according to claim 1, wherein the bacteria is at least one selected from the group consisting of cocci, bacilli and spirochetes.
3. The method for preparing the dual-template multi-stage porous carbon-based material according to claim 1, wherein the mesoporous silica layer/bacterial composite template is obtained by mixing and reacting bacterial liquid, tetraethyl orthosilicate and a template agent.
4. The method for preparing the dual-template multi-stage porous carbon-based material as claimed in claim 3, wherein OD of the bacterial liquid600nmThe value is 80 to 120.
5. The method for preparing the dual-template multi-stage porous carbon-based material according to claim 3, wherein the carbon source is polyaniline, and the synthesis method comprises the following steps: mixing the mesoporous silica layer/bacteria composite template with aniline, and reacting in the presence of an oxidant to synthesize polyaniline in the pore canal of the mesoporous silica layer.
6. The method for preparing the dual-template multi-stage porous carbon-based material according to claim 5, wherein the weight ratio of the bacteria, the tetraethyl orthosilicate and the aniline is 0.5:2.5:0.5 to 2.
7. The method for preparing a dual-template multi-stage porous carbon-based material according to claim 1, wherein the carbonization conditions are as follows: carbonizing at 600-900 ℃, wherein the heating rate is 2-10 ℃ per min, and the carbonizing time is 3-6 hours.
8. The method for preparing the dual-template multi-stage porous carbon-based material according to claim 1, wherein the protective atmosphere is at least one selected from the group consisting of nitrogen, helium and argon.
9. A dual-template multi-level porous carbon-based material, characterized in that it is obtained by the method according to any one of claims 1 to 8.
10. Use of the dual-template multi-stage porous carbon-based material of claim 9 in the preparation of an electrode material for a lithium sulfur battery.
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| CN102295281A (en) * | 2011-06-21 | 2011-12-28 | 华东理工大学 | Method for preparing graded porous carbon with hollow mesoporous silicon spheres as templates |
| CN103407986A (en) * | 2013-07-24 | 2013-11-27 | 上海应用技术学院 | Ellipsoidal nitrogen-doped mesoporous carbon, and preparation method and applications thereof |
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