CN112701266B - Preparation method and application of porous carbon and sulfur composite material - Google Patents
Preparation method and application of porous carbon and sulfur composite material Download PDFInfo
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- CN112701266B CN112701266B CN202011612826.5A CN202011612826A CN112701266B CN 112701266 B CN112701266 B CN 112701266B CN 202011612826 A CN202011612826 A CN 202011612826A CN 112701266 B CN112701266 B CN 112701266B
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Abstract
The invention discloses a preparation method of a porous carbon and sulfur composite material, which comprises the following steps: s1, placing the natural cotton in aniline hydrochloric acid water solution with silicon balls for 8-12h under the condition of 70 ℃ water bath; s2, putting the soaked cotton into a container under an ice bath condition, dropwise adding a hydrochloric acid aqueous solution of ammonium persulfate into the soaked cotton, and stirring for 20-24 hours by using a magnetic stirrer; s3, carrying out freeze-drying treatment on the mixture obtained in the S2; s4, calcining the mixture subjected to the S3 freeze-drying treatment; s5, etching the mixture calcined in the S4 twice by adopting ammonium bifluoride, and then drying; s6, putting 30 parts of the dried mixture in the S5 and 70 parts of elemental sulfur into a mortar for uniform grinding; and S7, adding 10 parts of PVDF liquid and 10 parts of acetylene black into the uniformly ground mixture in the step S6, and grinding the mixture into a slurry again to obtain the porous carbon-sulfur composite material. The lithium battery prepared by the composite material can effectively reduce shuttle effect.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to a preparation method and application of a porous carbon and sulfur composite material.
Background
The lithium-sulfur battery has very high theoretical specific capacity (1675mAh g-1) and theoretical specific energy (2600Wh kg-1), which are far higher than the traditional lithium ion battery, so the lithium-sulfur battery has attracted extensive attention and is considered to be one of the most promising secondary batteries. In addition, the system has high commercial value due to the characteristics of abundant elemental sulfur reserves, low price, safety, no toxicity and environmental friendliness. However, lithium sulfur batteries still face several challenges: on one hand, elemental sulfur and a reduction product thereof, namely lithium sulfide, have poor conductivity, and are easy to cause low utilization rate of active substances; on the other hand, the dissolution and diffusion of the intermediate product easily cause the loss of active materials and the damage of the lithium negative electrode, and the occurrence of the shuttle effect seriously restricts the cycle stability of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a preparation method of a porous carbon-sulfur composite material and an application thereof, and solves the problems that in the lithium-sulfur battery in the prior art, on one hand, elemental sulfur and a reduction product of the elemental sulfur have poor conductivity, the utilization rate of active substances is easy to cause low, and the loss of the active substances and the damage of a lithium cathode are easy to cause by the dissolution and diffusion of an intermediate product, so that the occurrence of shuttle effect seriously restricts the cycle stability of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a porous carbon and sulfur composite material comprises the following steps:
s1, placing the natural cotton in aniline hydrochloric acid water solution with silicon balls for 8-12h under the condition of 70 ℃ water bath;
s2, putting the soaked cotton into a container under an ice bath condition, dropwise adding a hydrochloric acid aqueous solution of ammonium persulfate into the soaked cotton, and stirring for 20-24 hours by using a magnetic stirrer;
s3, transferring the mixture obtained in the step S2 to a plastic beaker for freeze-drying treatment;
s4, calcining the mixture subjected to freeze-drying treatment in the step S3 at the temperature of 500-800 ℃ for 1-2 h;
s5, etching the mixture calcined in the step S4 twice by using ammonium bifluoride, and drying to obtain a porous carbon-carbon fiber material;
s6, taking 20-40 parts of the porous carbon-carbon fiber material dried in the step S5 and 60-80 parts of elemental sulfur, and uniformly grinding the porous carbon-carbon fiber material and the elemental sulfur in a mortar;
and S7, adding 10-20 parts of PVDF liquid and 10-20 parts of acetylene black into the uniformly ground mixture in the step S6, and grinding the mixture into a slurry again to obtain the porous carbon and sulfur composite material.
Further, the mass ratio of the natural cotton to the aniline in the step S1 is 1-3: 1; the mass ratio of the natural cotton to the silicon balls is 10-20: 1.
Further, the temperature of the ice bath in the step S2 is-15 to-20 ℃; the mass ratio of the soaked cotton to the ammonium persulfate is 1-3: 1.
Further, the calcination temperature in step S4 is 800 ℃ and the calcination time is 1 h.
Further, 30 parts of the porous carbon — carbon fiber material dried in step S5 in step S6 and 70 parts of elemental sulfur are taken.
The prepared porous carbon and sulfur composite material is applied as a lithium-sulfur battery positive electrode material, the slurry-like porous carbon and sulfur composite material prepared in the step S7 is uniformly stirred and then coated on a pole piece, the pole piece coated with the porous carbon and sulfur composite material is placed in a vacuum drying oven and dried at the temperature of 60-80 ℃ for 10-12 hours, and then the pole piece is assembled on the lithium-sulfur battery.
The invention utilizes natural cotton and aniline to prepare a porous carbon-carbon fiber material in a branch-leaf shape by a simple in-situ polymerization method, zero-dimensional porous carbon is uniformly distributed on the surface of one-dimensional carbon fiber, the carbon fiber is a branch, the porous carbon is a leaf, the zero-dimensional porous carbon has good conductivity and larger surface area, can contain more elemental sulfur and polysulfide, effectively relieves the problem of poor conductivity of elemental sulfur and reduced product lithium sulfide thereof, and a pore passage of the porous carbon can restrict the polysulfide to a certain extent and inhibit a shuttle effect; the one-dimensional carbon fiber can contain elemental sulfur and intermediate products thereof, and the limitation of short-range conductivity of pure porous carbon is greatly relieved by long-range conductivity of the one-dimensional carbon fiber, the multi-dimensional carbon nano composite material provides enhanced conductivity through increased electric contact parts, an effective multi-dimensional transmission channel is provided for electrons and ions, and compared with the existing porous carbon and sulfur composite material, the cycling stability of the lithium-sulfur battery is greatly improved.
Drawings
FIG. 1 is a transmission electron microscope image of a porous carbon-carbon fiber material prepared in an embodiment of the present invention;
FIG. 2 is a graph comparing the cycle performance of porous carbon and sulfur composite materials prepared in the embodiments of the present invention as a lithium-sulfur battery cathode material with that of conventional materials;
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
A preparation method of a porous carbon and sulfur composite material comprises the following steps:
s1, placing natural cotton into an aniline hydrochloric acid aqueous solution added with silicon balls, and standing for 12 hours under the condition of a water bath at 70 ℃, wherein the mass ratio of the natural cotton to the aniline is 3:1, and the mass ratio of the natural cotton to the silicon balls is 10: 1;
s2, placing the soaked cotton into a container under an ice bath condition, dropwise adding a hydrochloric acid aqueous solution of ammonium persulfate into the soaked cotton, and stirring for 24 hours by using a magnetic stirrer, wherein the temperature of the ice bath is-15 ℃; the mass ratio of the soaked cotton to the ammonium persulfate is 3: 1;
s3, transferring the mixture obtained in the step S2 to a plastic beaker for freeze-drying treatment;
s4, calcining the mixture subjected to freeze-drying treatment in the step S3 at 800 ℃ for 1 h;
s5, etching the mixture calcined in the step S4 twice by using ammonium bifluoride, and drying to obtain a porous carbon-carbon fiber material, wherein a transmission electron microscope image of the porous carbon-carbon fiber material is shown in figure 1;
s6, taking 30 parts of the porous carbon-carbon fiber material dried in the step S5 and 70 parts of elemental sulfur, and uniformly grinding the materials in a mortar;
s7, adding 10 parts of PVDF liquid and 10 parts of acetylene black into the mixture uniformly ground in the step S6, and grinding again into a slurry to obtain the porous carbon-sulfur composite material.
The porous carbon and sulfur composite material prepared in the step is applied as a lithium sulfur battery positive electrode material, the slurry-like porous carbon and sulfur composite material prepared in the step S7 is uniformly stirred and then coated on a pole piece, the pole piece coated with the porous carbon and sulfur composite material is placed in a vacuum drying oven, and after drying is carried out for 12 hours at the temperature of 60 ℃, the pole piece is finally assembled on the lithium sulfur battery. The cycle performance of the lithium sulfur battery is compared with that of the conventional lithium sulfur battery as shown in fig. 2. As can be seen from FIG. 2, under the current density of 0.1C, the first discharge specific capacity of the cathode of the lithium-sulfur battery manufactured by using the traditional porous carbon and sulfur composite material as the anode is 1113.7mAh g < -1 >, and the capacity is reduced to 380.9mAh g < -1 > after 100 cycles of circulation, compared with the lithium battery manufactured by using the porous carbon and sulfur composite material as the anode material, the first charge-discharge specific capacity of the cathode of the lithium battery is increased to 1143mAh g < -1 >, and the specific capacity can still be maintained at 679.5mAh g < -1 > after 100 cycles of circulation, so that the circulation stability is greatly improved, and the coulombic efficiency is always maintained above 99%.
The invention utilizes natural cotton and aniline to prepare a porous carbon-carbon fiber material in a branch-leaf shape by a simple in-situ polymerization method, zero-dimensional porous carbon is uniformly distributed on the surface of one-dimensional carbon fiber, the carbon fiber is a branch, the porous carbon is a leaf, the zero-dimensional porous carbon has good conductivity and larger surface area, can contain more elemental sulfur and polysulfide, effectively relieves the problem of poor conductivity of elemental sulfur and reduced product lithium sulfide thereof, and a pore passage of the porous carbon can restrict the polysulfide to a certain extent and inhibit a shuttle effect; the one-dimensional carbon fiber can contain elemental sulfur and intermediate products thereof, and the limitation of short-range conductivity of pure porous carbon is greatly relieved by long-range conductivity of the one-dimensional carbon fiber, the multi-dimensional carbon nano composite material provides enhanced conductivity through increased electric contact parts, an effective multi-dimensional transmission channel is provided for electrons and ions, and compared with the existing porous carbon and sulfur composite material, the cycling stability of the lithium-sulfur battery is greatly improved.
The above-described embodiments are illustrative of the present invention and not restrictive, it being understood that various changes, modifications, substitutions and alterations can be made herein without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims (6)
1. A preparation method of a porous carbon and sulfur composite material is characterized by comprising the following steps:
s1, placing the natural cotton in aniline hydrochloric acid water solution with silicon balls for 8-12h under the condition of 70 ℃ water bath;
s2, putting the soaked cotton into a container under an ice bath condition, dropwise adding a hydrochloric acid aqueous solution of ammonium persulfate into the soaked cotton, and stirring for 20-24 hours by using a magnetic stirrer;
s3, transferring the mixture obtained in the step S2 to a plastic beaker for freeze-drying treatment;
s4, calcining the mixture subjected to freeze-drying treatment in the step S3 at the temperature of 500-800 ℃ for 1-2 h;
s5, etching the mixture calcined in the step S4 twice by adopting ammonium bifluoride, and drying to obtain the porous carbon-carbon fiber material;
s6, taking 20-40 parts of the porous carbon-carbon fiber material dried in the step S5 and 60-80 parts of elemental sulfur, and uniformly grinding the porous carbon-carbon fiber material and the elemental sulfur in a mortar;
and S7, adding 10-20 parts of PVDF liquid and 10-20 parts of acetylene black into the uniformly ground mixture in the step S6, and grinding the mixture into a slurry again to obtain the porous carbon and sulfur composite material.
2. The preparation method of the porous carbon-sulfur composite material according to claim 1, wherein the mass ratio of the natural cotton to the aniline in the step S1 is 1-3: 1; the mass ratio of the natural cotton to the silicon balls is 10-20: 1.
3. The preparation method of the porous carbon and sulfur composite material according to claim 1, wherein the temperature of the ice bath in the step S2 is-15 to-20 ℃; the mass ratio of the soaked cotton to the ammonium persulfate is 1-3: 1.
4. The method for preparing a porous carbon-sulfur composite material according to claim 1, wherein the calcination temperature in step S4 is 800 ℃ and the calcination time is 1 hour.
5. The method for preparing a porous carbon-sulfur composite material according to claim 1, wherein 30 parts of the porous carbon-carbon fiber material dried in step S5 and 70 parts of elemental sulfur are taken in step S6.
6. The application of the porous carbon and sulfur composite material prepared by the preparation method according to any one of claims 1 to 5 as the positive electrode material of the lithium-sulfur battery is characterized in that the slurry-like porous carbon and sulfur composite material prepared in the step S7 is uniformly stirred and coated, then the pole piece coated with the porous carbon and sulfur composite material is placed in a vacuum drying oven, and after drying is carried out for 10 to 12 hours at the temperature of 60 to 80 ℃, the pole piece is assembled on the lithium-sulfur battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107845780A (en) * | 2016-09-18 | 2018-03-27 | 中国科学院大连化学物理研究所 | The solvent heat assistant preparation method of lithium-sulfur cell carbon-sulfur compound positive electrode |
| CN109244413A (en) * | 2018-09-21 | 2019-01-18 | 合肥工业大学 | A kind of sulphur anode composite material and preparation method thereof based on multiporous biological matter carbon |
| CN109301135A (en) * | 2018-11-24 | 2019-02-01 | 中国科学院青岛生物能源与过程研究所 | It is a kind of for improving the preparation method of the modified diaphragm of lithium-sulfur cell chemical property |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103187560B (en) * | 2013-03-30 | 2016-02-24 | 浙江工业大学 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
| US10446329B2 (en) * | 2015-09-23 | 2019-10-15 | University Of Virginia Patent Foundation | Process of forming electrodes and products thereof from biomass |
| CN105633372B (en) * | 2016-01-22 | 2019-07-05 | 复旦大学 | Nickel sulfide nanoparticles/N doping fiber base carbon aerogel composite material and preparation method thereof |
| CN106356513B (en) * | 2016-11-02 | 2018-11-23 | 武汉理工大学 | A kind of preparation method of the conducting polymer with sandwich structure/sulphur composite positive pole |
| CN108123110B (en) * | 2016-11-28 | 2020-09-04 | 中国科学院大连化学物理研究所 | Preparation method and application of nitrogen-containing large-pore-volume porous carbon material |
| CN107946582B (en) * | 2017-12-01 | 2020-09-08 | 江苏海四达电源股份有限公司 | Lithium-sulfur battery positive electrode material, preparation method thereof, lithium battery positive electrode and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107845780A (en) * | 2016-09-18 | 2018-03-27 | 中国科学院大连化学物理研究所 | The solvent heat assistant preparation method of lithium-sulfur cell carbon-sulfur compound positive electrode |
| CN109244413A (en) * | 2018-09-21 | 2019-01-18 | 合肥工业大学 | A kind of sulphur anode composite material and preparation method thereof based on multiporous biological matter carbon |
| CN109301135A (en) * | 2018-11-24 | 2019-02-01 | 中国科学院青岛生物能源与过程研究所 | It is a kind of for improving the preparation method of the modified diaphragm of lithium-sulfur cell chemical property |
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