CN113764635A - One-step hydrothermal preparation method and application of sulfur-carbon composite material - Google Patents
One-step hydrothermal preparation method and application of sulfur-carbon composite material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a one-step hydrothermal preparation method and application of a sulfur-carbon composite material. The invention utilizes the solubility of elemental sulfur in hot water and the carbonization process of organic molecules under the high-temperature hydrothermal condition to attach the elemental sulfur in situ in the generation process of the carbon material, and realizes the preparation of the sulfur-carbon composite material with the elemental sulfur uniformly distributed in the carbon material bulk phase by the bottom-up assembly process. Compared with the traditional two-step preparation method, the method can realize the design of the sulfur-carbon composite material through one-step hydrothermal method, and uses water as a solvent, thereby not only being green and environment-friendly and greatly reducing the cost, but also being simple to operate and being beneficial to realizing industrial production. In addition, the invention takes water as solvent, has lower cost and has great application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a one-step hydrothermal preparation method and application of a sulfur-carbon composite material, in particular to a one-step hydrothermal preparation method of a sulfur-carbon composite material by taking organic molecules and elemental sulfur as raw materials.
Background
With the increasing popularization of various electronic products in daily life of people, the social demand on energy is also increasing, and the increasing energy demand of the human society is difficult to meet by using the traditional lithium ion battery (the energy density is lower than 350Wh/kg) which takes lithium manganate, lithium cobaltate and other lithium-containing transition metal oxides as the positive electrode and carbon as the negative electrode. Therefore, the development of new energy storage systems with high energy density is imminent. Among them, lithium sulfur batteries using elemental sulfur as the positive electrode and metal lithium as the negative electrode have attracted extensive research interest in the industry and scientific research community because of their extremely high theoretical energy density (2600 Wh/kg). However, the lithium-sulfur battery is difficult to be applied to actual production and life because of the problems of extremely low conductivity of elemental sulfur as a positive energy storage component, dissolution and diffusion of lithium polysulfide as an intermediate product, volume expansion of an active material in the charging and discharging processes, and the like.
In order to overcome the defects of the sulfur electrode, the elemental sulfur is compounded with the porous carbon carrier with rich surface structure to improve the electron transfer efficiency of the elemental sulfur, and the diffusion loss of lithium polysulfide is inhibited by utilizing the porous structure and the functional groups on the surface of the composite material through physical and chemical adsorption to become an effective sulfur electrode modification means. At present, the preparation of an ideal sulfur-carbon composite material generally needs two steps of carbon material preparation and hot melting and compounding of elemental sulfur and a carbon carrier. In the preparation of carbon materials, it is generally necessary to treat a carbon source at a high temperature for a long time to prepare a functionalized carbon support; in the hot melting compounding process, elemental sulfur and a carbon carrier are ground and mixed, then the mixture is transferred into a closed container filled with inert gas, and the mixture is heated for 12 to 24 hours at the temperature of 155 ℃ to finally obtain the sulfur-carbon composite material. However, due to the diffusion resistance of liquid sulfur in the carbon pore channels, the uniform distribution of elemental sulfur in the carbon material is difficult to realize by the melting sulfur filling method, and the two-step preparation process of the sulfur-carbon composite material is long in time consumption and complicated in steps, so that the industrial requirement is difficult to meet. Therefore, there is an urgent need in the art to develop a simple and efficient preparation method of sulfur-carbon composite material to promote the industrial development of lithium-sulfur batteries.
Disclosure of Invention
In order to improve the technical problem, the invention provides a one-step preparation method of a sulfur-carbon composite material, which comprises the steps of taking elemental sulfur and organic molecules as raw materials, carrying out carbonization process in a water solvent under a high-temperature hydrothermal condition, and attaching the elemental sulfur in situ in the generation process of a carbon material to prepare the sulfur-carbon composite material.
According to an embodiment of the present invention, the organic molecule may be one of a small organic molecule or a large organic molecule.
According to an embodiment of the present invention, the organic small molecule may be at least one of glucose, fructose, sucrose, xylose, cyclodextrin, and the like, for example.
According to one embodiment of the present invention, the organic macromolecule may be, for example, at least one of starch, chitosan, and the like.
According to an embodiment of the present invention, the elemental sulfur includes at least one of sublimed sulfur, nano sulfur, and other elemental sulfur with different morphologies.
According to an embodiment of the invention, the mass ratio of elemental sulphur, organic molecule and water is (0.1-1): 20-100, exemplary 0.1:0.1:20, 0.1:1:20, 0.2:0.4:20, 0.2:0.6:20, 0.1:1:100, 1:1:20, 1:1: 100.
According to an embodiment of the present invention, the temperature of the hydrothermal reaction is 100-.
According to an embodiment of the invention, the hydrothermal reaction is carried out for 2-24h, exemplary 2h, 4h, 6h, 8h, 10h, 12h, 15h, 18h, 24 h.
According to an embodiment of the present invention, before the hydrothermal reaction, the method further comprises dispersing elemental sulfur and the organic molecule in water. For example, the dispersion means includes one, two or more of ball milling, ultrasonic and mechanical stirring.
According to the embodiment of the invention, the preparation method further comprises the step of carrying out solid-liquid separation on the reaction system after the reaction is finished to obtain a reaction product. For example, the solid-liquid separation may be performed by removing the solvent by means known in the art, such as filtration or suction filtration, to obtain a sulfur-carbon composite.
According to an embodiment of the present invention, the one-step preparation method of the sulfur-carbon composite material comprises the steps of:
(1) preparing a precursor suspension: dispersing elemental sulfur and organic molecules in water to prepare a precursor suspension;
(2) high-temperature hydrothermal process: and (2) transferring the suspension obtained in the step (1) into a hydrothermal reaction kettle, controlling the reaction temperature at 100 ℃ and 200 ℃, reacting for 2-24h, and removing the solvent by methods such as filtration or suction filtration after the hydrothermal process is finished to obtain the sulfur-carbon composite material.
The invention also provides the sulfur-carbon composite material prepared by the method.
According to an embodiment of the present invention, the sulfur-carbon composite material has a sulfur content of 35 to 76%, illustratively 37%, 50%, 60%, 70%, 76%.
The invention also provides application of the sulfur-carbon composite material in a lithium-sulfur battery.
The invention also provides a lithium-sulfur battery which contains the sulfur-carbon composite material.
According to an embodiment of the present invention, the battery further comprises conductive carbon black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder.
According to the embodiment of the invention, in the battery, the mass ratio of the sulfur-carbon composite material to the conductive agent to the adhesive is (8-0): 1-9): 1.
The invention has the beneficial effects that:
(1) the invention provides a simple and efficient one-step preparation method of a sulfur-carbon composite material, which utilizes the soluble combination of elemental sulfur in hot water and an organic molecule in the carbonization process under the high-temperature hydrothermal condition to attach the elemental sulfur in situ in the generation process of a carbon material, and realizes the preparation of the uniform sulfur-carbon composite material by the assembly process from bottom to top. Compared with the traditional two-step preparation method, the method can realize the design of the sulfur-carbon composite material through one-step hydrothermal method, and uses water as a solvent, thereby not only being green and environment-friendly and greatly reducing the cost, but also being simple to operate and being beneficial to realizing industrial production. In addition, the invention takes water as solvent, has lower cost and has great application prospect.
(2) The invention utilizes the solubility of elemental sulfur in hot water and combines the carbonization process of organic molecules under hydrothermal conditions to realize the in-situ adhesion of elemental sulfur molecules in the formation process of carbon materials. And (4) obtaining the sulfur-carbon composite material with the elemental sulfur uniformly distributed in the carbon material bulk phase along with the end of the carbonization process.
Drawings
FIG. 1 is a scanning electron microscope photograph of the sulfur-carbon composite material prepared in example 2.
FIG. 2 is a cyclic voltammogram of the sulfur-carbon composite prepared in example 3 at a sweep rate of 0.1 mV/s.
Fig. 3 is a charge and discharge curve of the sulfur-carbon composite material prepared in example 3 at a current of 0.2C.
Fig. 4 is a graph showing the discharge capacity of the sulfur-carbon composite material prepared in example 3 at different currents.
Fig. 5 shows the results of the cycle stability test of the sulfur-carbon composite material prepared in example 3 at a current of 1.0C.
Fig. 6 is a scanning electron microscope (left image) of the sulfur-carbon composite material prepared in example 3 and the distribution state of two elements of sulfur and carbon therein (right image).
Fig. 7 is a result of a cycle stability test of the sulfur-carbon composite material prepared in comparative example 1 at a current of 1.0C.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
A one-step hydrothermal preparation method of a sulfur-carbon composite material comprises the following steps:
0.2g of sublimed sulfur and 0.2g of glucose were first sonicated in 20mL of water for 10min and magnetically stirred for 30min to obtain a homogeneous suspension. The suspension was then transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 180 ℃ for 10 h. And after the reaction kettle is cooled to room temperature, removing the solvent through suction filtration to obtain the sulfur-carbon composite material.
Example 2
A one-step hydrothermal preparation method of a sulfur-carbon composite material comprises the following steps:
0.2g of sublimed sulfur and 0.4g of glucose were first sonicated in 20mL of water for 10min and magnetically stirred for 30min to obtain a homogeneous suspension. The suspension was then transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 160 ℃ for 8 h. And after the reaction kettle is cooled to room temperature, removing the solvent through suction filtration to obtain the sulfur-carbon composite material.
The sulfur-carbon composite material prepared in example 2 was observed by a cold field emission scanning electron microscope, and the results are shown in fig. 1. As can be seen from the figure: the sulfur-carbon composite material obtained by the hydrothermal method exists in the form of agglomerated nano particles.
Example 3
A one-step hydrothermal preparation method of a sulfur-carbon composite material comprises the following steps:
0.2g of sublimed sulfur and 0.6g of glucose were first sonicated in 20mL of water for 10min and magnetically stirred for 30min to obtain a homogeneous suspension. The suspension was then transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 160 ℃ for 4 h. And after the reaction kettle is cooled to room temperature, removing the solvent through suction filtration to obtain the sulfur-carbon composite material.
Comparative example 1
A preparation method of a sulfur-carbon composite material comprises the following steps:
first, 0.6g of glucose was dissolved in 20mL of distilled water to obtain a uniform glucose solution. Then transferring the glucose solution into a 50mL hydrothermal reaction kettle, and carrying out hydrothermal reaction for 4h at 160 ℃ to obtain the carbon material. Mixing and grinding the prepared carbon material and 0.2g of sublimed sulfur for 30min, placing the mixture in a 50mL hydrothermal reaction kettle filled with nitrogen, and heating at 155 ℃ for 12h to obtain the sulfur-carbon composite material.
The sulfur-carbon composite materials prepared in example 3 and comparative example 1, conductive carbon black and polyvinylidene fluoride (PVDF) were dispersed in N-methylpyrrolidone (NMP) at a mass ratio of 7:2:1, respectively, and were subjected to ultrasonic treatment for 30min and magnetic stirring for 24 hours to prepare a uniform slurry. Respectively coating the obtained slurry on aluminum foils, carrying out vacuum drying at 50 ℃ for 24h, cutting the aluminum foils into round sheets with the diameter of 12mm as the positive electrode of the lithium-sulfur battery after NMP is completely volatilized, taking metal lithium as the negative electrode, and taking 2 wt% LiNO as the negative electrode3Dissolving +1mol/L LiTFSI in a mixed solvent of DOL + DME (the volume ratio of DOL to DME is 1:1) to serve as electrolyte, wherein the diaphragm is a commercialized Celegard 2400 diaphragm, respectively assembling 2025 button cells in an inert atmosphere glove box, and testing a cyclic voltammetry curve by using an electrochemical workstation of Shanghai Chenghua CHI 760E; the multiplying power performance and the cycling stability of the battery are tested in a voltage range of 1.7-2.8V by a blue battery test system.
FIG. 2 is a cyclic voltammogram of the electrode prepared in example 3 at a sweep rate of 0.1mV/s, showing the appearance of two distinct reduction peaks near 2.3V and 2.05V in the negative-going scan, corresponding to the characteristic peaks of elemental sulfur conversion to lithium polysulfide and lithium polysulfide conversion to lithium sulfide, respectively; whereas during the corresponding forward scan a set of overlapping oxidation peaks appears around 2.4V, corresponding to a continuous process of conversion of lithium sulphide to elemental sulphur.
Fig. 3 is a charge-discharge curve at 0.2C current of a battery made of the sulfur-carbon composite material prepared in example 3, wherein the charge-discharge curve shows an electrochemical process similar to a cyclic voltammetry curve, and is identical to the elemental sulfur energy storage mechanism reported in the prior art (fig. 7 is the cyclic performance at 1.0C current of the sulfur-carbon composite material prepared in comparative example 1). The above results show that: the sulfur-carbon composite material synthesized by one step through the hydrothermal process has the same energy storage mechanism as the sulfur-carbon composite material synthesized by multiple steps in the prior art, and the method has simple step operation, can replace fussy operation steps in documents, and has great development potential.
Fig. 4 is a graph of rate performance of a battery made from the sulfur-carbon composite prepared in example 3, showing the results: the sulfur-carbon composite material prepared in example 3 can show initial capacity close to 870mAh/g under the current of 0.2C, and when the current is increased to 2.0C, the discharge capacity of the battery can still be kept at about 400 mAh/g.
The batteries manufactured from the sulfur-carbon composites manufactured in example 3 and comparative example 1 were subjected to cycle life tests with a current of 1.0C, and the results are shown in fig. 5 and 7, respectively. As can be seen from the figure: after 100 cycles, the capacity of the battery prepared by using the sulfur-carbon composite material prepared in example 3 as an active material was maintained at 385.1mAh/g, which is much higher than the capacity (197.8mAh/g) of the battery prepared by using the sulfur-carbon composite material prepared in comparative example 1 as an active material. This indicates that: compared with the sulfur-carbon composite material prepared by the traditional multi-step method, the sulfur-carbon composite material prepared by the one-step method has more excellent cycle stability.
Example 4
A one-step hydrothermal preparation method of a sulfur-carbon composite material comprises the following steps:
first 0.2g sublimed sulfur and 1.2g glucose were sonicated in 20mL water for 10min and magnetically stirred for 30min to obtain a homogeneous suspension. The suspension was then transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 150 ℃ for 10 h. And after the reaction kettle is cooled to room temperature, removing the solvent through suction filtration to obtain the sulfur-carbon composite material.
The sulfur-carbon composite materials obtained in example 1, example 2 and example 4 were all able to prepare lithium-sulfur batteries and had substantially the same properties as example 3.
The results show that: the one-step hydrothermal preparation process of the sulfur-carbon composite material has the characteristics of simplicity in operation, low cost, easiness in industrialization and the like, and the prepared sulfur-carbon composite material has good electrochemical performance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The one-step preparation method of the sulfur-carbon composite material is characterized by comprising the steps of taking elemental sulfur and organic molecules as raw materials, carrying out carbonization in a water solvent under a high-temperature hydrothermal condition, and attaching the elemental sulfur in situ in the generation process of a carbon material to prepare the sulfur-carbon composite material.
2. The method of claim 1, wherein the organic molecule is one of a small organic molecule or a large organic molecule.
Preferably, the organic small molecule may be at least one of glucose, fructose, sucrose, xylose, cyclodextrin, and the like, for example.
Preferably, the organic macromolecule may be, for example, at least one of starch, chitosan, and the like.
Preferably, the elemental sulfur includes at least one of sublimed sulfur, nano sulfur and other elemental sulfur with different morphologies.
3. The method according to claim 1 or 2, wherein the mass ratio of elemental sulfur, organic molecule and water is (0.1-1): (20-100).
4. The production method according to any one of claims 1 to 3, wherein the temperature of the hydrothermal reaction is 100-200 ℃.
Preferably, the hydrothermal reaction is carried out for 2-24 h.
5. The method of any one of claims 1-4, further comprising dispersing elemental sulfur and the organic molecule in water prior to the hydrothermal reaction.
Preferably, the dispersion means comprises one, two or more of ball milling, ultrasound and mechanical stirring.
6. The production method according to any one of claims 1 to 5, further comprising a step of subjecting the reaction system to solid-liquid separation to obtain a reaction product after the completion of the reaction.
7. The method of any one of claims 1 to 6, wherein the one-step preparation of the sulfur-carbon composite material comprises the steps of:
(1) preparing a precursor suspension: dispersing elemental sulfur and organic molecules in water to prepare a precursor suspension;
(2) high-temperature hydrothermal process: and (2) transferring the suspension obtained in the step (1) into a hydrothermal reaction kettle, controlling the reaction temperature at 100-200 ℃, the reaction time at 2-24h and the pressure at 1-10MPa, and removing the solvent by methods such as filtration or suction filtration after the hydrothermal process is finished to obtain the sulfur-carbon composite material.
8. The sulfur-carbon composite material produced by the production method according to any one of claims 1 to 7.
Preferably, the sulfur-carbon composite material has a sulfur content of 35-76%.
9. Use of the sulfur-carbon composite of claim 8 in a lithium sulfur battery.
10. A lithium sulfur battery comprising the sulfur-carbon composite material of claim 8.
Preferably, the battery also comprises a conductive agent, conductive carbon black and a binder, namely polyvinylidene fluoride (PVDF).
Preferably, in the battery, the mass ratio of the sulfur-carbon composite material to the conductive agent to the adhesive is (8-0): 1-9): 1.
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| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
| 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 |
| CN107959001A (en) * | 2016-10-18 | 2018-04-24 | 福建新峰二维材料科技有限公司 | The preparation method and lithium sulphur/carbon battery of a kind of sulphur/carbon composite anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
| 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 |
| CN107959001A (en) * | 2016-10-18 | 2018-04-24 | 福建新峰二维材料科技有限公司 | The preparation method and lithium sulphur/carbon battery of a kind of sulphur/carbon composite anode material |
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Application publication date: 20211207 |