CN109273272B - Preparation method of sulfur-doped carbon micro-tube, sulfur-doped carbon micro-tube and application of sulfur-doped carbon micro-tube - Google Patents
Preparation method of sulfur-doped carbon micro-tube, sulfur-doped carbon micro-tube and application of sulfur-doped carbon micro-tube Download PDFInfo
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- CN109273272B CN109273272B CN201811019127.2A CN201811019127A CN109273272B CN 109273272 B CN109273272 B CN 109273272B CN 201811019127 A CN201811019127 A CN 201811019127A CN 109273272 B CN109273272 B CN 109273272B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a sulfur-doped carbon micro-tube, the sulfur-doped carbon micro-tube and application thereof2Carbonizing and vulcanizing the mixture in an S/Ar atmosphere to obtain the sulfur-doped carbon micron tube. The method for preparing the sulfur-doped carbon nanotube takes cotton as a raw material and obtains the sulfur-doped carbon nanotube material through one-step pyrolysis. The method has the advantages of simple process, green and environment-friendly used raw materials, suitability for batch production, strong repeatability and low cost, sulfur doping and carbonization can be realized through one-step reaction, the sulfur doping is more uniform through the doping of hydrogen sulfide gas at high temperature, and the natural cotton can be used without any purification treatment. The sulfur-doped carbon nanotube prepared by the method generates a large amount of nano holes on the surface, has a large specific surface area and excellent electrochemical performance, and can be used as an ideal cathode material of a sodium-ion battery.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method of a sulfur-doped carbon micro-tube, a sulfur-doped carbon micro-tube prepared by the preparation method and application of the sulfur-doped carbon micro-tube.
Background
In the field of large-scale energy storage, sodium ion batteries are receiving more and more attention as one of the most potential substitutes of lithium ion batteries mainly because of the advantages of abundant resources, environmental friendliness and the like. However, due to the radius of sodium ions
Greater than the radius of lithium ion
Resulting in more sluggish diffusion kinetics of sodium ions. Some sodium ion battery host materials reported at present include carbon-based materials, titanium-based materials, alloy-type materials, and metal oxide/sulfide materials, etc., which all exhibit good sodium storage properties, but their cycle stability is not satisfactory.
In recent years, the porous carbon nano structure is constructed to make great progress in the cycling stability of the sodium-ion battery. In addition, doping of heteroatoms such as nitrogen, boron, sulfur, and phosphorus has also received great attention as an effective measure for improving the sodium storage performance of the carbon-based material. Sulfur is a highly electrochemically active element that can react reversibly with sodium. Thus, the introduction of sulfur into carbon materials may add additional sodium storage sites, resulting in an increase in reversible capacity.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of a sulfur-doped carbon nanotube, which is environment-friendly and simple in process, and can obtain a sulfur-doped carbon nanotube material through one-step pyrolysis.
The invention also provides a sulfur-doped carbon nanotube material and application thereof.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing a sulfur-doped carbon nanotube, comprising the steps of: direct cotton grafting in H by one-step reaction2And carbonizing and vulcanizing the mixture in the S/Ar atmosphere to obtain the sulfur-doped carbon micron tube.
Preferably, said H is2In an S/Ar atmosphere, H2The volume percentage of the S gas is 5-10%.
And the carbonization and vulcanization are carried out by placing the cotton into a tube furnace, heating the tube furnace to 600-800 ℃ at the speed of 2-10 ℃/min, and then keeping the temperature for 2-3 h.
Preferably, the hydrogen sulfide gas is doped at the high temperature of 600-800 ℃ so that the sulfur doping is more uniform.
Wherein the cotton is natural cotton and can be used without any purification treatment.
Further, the amount of the cotton is 1-2 g.
The sulfur-doped carbon micro-tube prepared by the preparation method of the sulfur-doped carbon micro-tube is provided.
After the sulfur-doped carbon micron tube is doped with sulfur, a large number of nano holes are generated on the surface of the cotton-derived carbon micron tube, and the specific surface area is large.
The sulfur-doped carbon micro-tube prepared by the preparation method of the sulfur-doped carbon micro-tube is applied as a negative electrode material of a sodium ion battery.
The invention uses cotton as a precursor, in H2Preparing several carbon micron tube materials in S/Ar or Ar atmosphere, and researching their sodium storage performance. Experiments show that the sulfur-doped carbon nanotube has higher reversible specific capacity when being used as a negative electrode material of a sodium ion battery, and is a high-performance negative electrode material of the sodium ion battery.
The preparation method takes cotton widely existing in nature as raw material, and the cotton is put in H2And vulcanizing and carbonizing in an S/Ar atmosphere to obtain the sulfur-doped carbon micron tube and carbonizing in an Ar atmosphere to obtain the carbon micron tube. Testing the components of the obtained sulfur-doped carbon micron tube by adopting an X-ray diffractometer (XRD) and an infrared spectrum (FT-IR); the size, morphology, microstructure, and the like of the obtained sulfur-doped carbon nanotube were observed by a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), and a high-resolution transmission electron microscope (HRTEM). The results show that the sulfur-doped carbon nanotube has a rough surface and a large size.
The invention adopts H2S/Ar is used for directly vulcanizing cotton and simultaneously carrying out carbonization treatment, the raw material cotton does not need to be subjected to any purification treatment, the method is simple and easy to implement, and the specific surface area of the obtained product is larger and is 307.6m2g-1And a large number of micropores are present; the biomass-derived carbon materials in the prior art have smaller specific surface areas.
Therefore, the sulfur-doped carbon material obtained by the invention has larger specific surface area, shows excellent rate performance when being used as a cathode material of a sodium ion battery, a discharge curve can be divided into two areas, and a high-voltage part (0.83-2V) is used for storing sodium by strong bonding of sodium and sulfur; the low voltage part (less than 0.83V) comprises disordered nanocrystalline surface defect sodium storage and intercalation sodium storage between graphene sheets. Compared with the undoped carbon microtubes, the sulfur-doped carbon microtubes have a higher specific capacity than the undoped carbon microtubes even in the low-voltage platform region, because of the introduction of a large number of micropores by sulfur doping, sodium storage is facilitated. In addition, the precursor of the material obtained by the invention is biomass cotton and the sulfur source is hydrogen sulfide gas; in the prior art, the similar sulfur-doped carbon material is vulcanized by using glucose or carbon-containing organic matters as carbon precursors and using sulfur powder as a sulfur source, and the precursors and the selected sulfur source or the vulcanization mode of the precursors are completely different.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the method for preparing the sulfur-doped carbon nanotube takes cotton as a raw material and obtains the sulfur-doped carbon nanotube material through one-step pyrolysis. The method has the advantages of simple process, green and environment-friendly used raw materials, suitability for batch production, strong repeatability and low cost, sulfur doping and carbonization can be realized through one-step reaction, the sulfur doping is more uniform through the doping of hydrogen sulfide gas at high temperature, and the natural cotton can be used without any purification treatment.
(2) The sulfur-doped carbon nanotube prepared by the method generates a large amount of nano holes on the surface, has a large specific surface area and excellent electrochemical performance, and can be used as an ideal cathode material of a sodium-ion battery.
Drawings
FIG. 1 is an SEM image of a sulfur-doped carbon nanotube, where it can be observed that the average size of the sulfur-doped carbon nanotube is about 8-14 μm;
FIG. 2 is a HRTEM image of a sulfur-doped carbon nanotube showing that the resulting carbon material contains a large number of nanopores and the surface of the nanotube is relatively rough;
FIG. 3 is an XRD pattern of sulfur-doped carbon nanotubes (S-CMTs) showing that characteristic peaks of carbon appear at 23.8 and 43.7 corresponding to (002) and (101) crystal planes, respectively, consistent with the results observed by HRTEM and no diffraction peaks of elemental sulfur and pure cotton;
FIG. 4 is a FT-IR chart of S-CMTs at-1344 and-881 cm-1The absorption peaks observed in the method can be attributed to the stretching vibration of the C-S bond and the S-S bond, and the sulfur is doped into the carbon structure; at 1167cm-1The absorption peak of (A) is the stretching vibration of the C-O bond, which indicates that an aromatic ring structure with a plurality of defects is formed on the surface of the S-CMTs.
FIG. 5 is a graph of the charge/discharge curves for S-CMTs. The figure shows that the first cycle charge and discharge capacity is 532 and 850mAh g respectively-1Storehouse (laboratory)The efficiency is about 62.6%; the irreversible capacity loss of the first turn (37.4%) is caused by the decomposition of the electrolyte and the formation of a solid electrolyte membrane on the surface of the carbon micro-tube;
FIG. 6 is a graph of the performance of S-CMTs magnification. The rate capability plot shows that S-CMTs are capable of high current densities, e.g., 5 and 10Ag-1The specific capacity can still be respectively kept at 199 and 140mAh g-1；
FIG. 7 is a graph of the cycling performance of undoped carbon nanotubes (CMTs) obtained by carbonizing S-CMTs and cotton at 700 ℃ under an argon atmosphere. Specifically, the voltage range is 0.01-3V, and the current density is 1A g-1Under the condition that the reversible capacity of S-CMTs and CMTs after 1000 cycles is 281mAh g respectively-1And 59.6mAh g-1The results show that the specific capacity of S-CMTs is much higher than that of CMTs.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
(1) Preparation of sulfur-doped carbon nanotubes (S-CMTs)
2g of cotton are weighed into a porcelain boat and transferred into a tube furnace in H2In an S/Ar atmosphere, H2The volume percentage of S gas is 10%, the temperature is raised to 700 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 3h, so that black S-CMTs are obtained.
(2) Characterization of S-CMTs
The resulting S-CMTs were analyzed for size, morphology and microstructure using SEM, XRD and HRTEM images. FIG. 1 is an SEM image of S-CMTs showing that the diameter of the sulfur doped carbon nanotubes is about 8-14 μm; FIG. 2 is an HRTEM image of S-CMTs showing that the S-CMTs have a rough surface and a large number of nanopores.
The composition of the resulting S-CMTs was tested by XRD. FIG. 3 is an XRD pattern of S-CMTs, in which two distinct broad peaks at 23.8 ℃ and 43.7 ℃ are observed, corresponding to (002) and (101) crystal planes of S-CMTs, demonstrating that the carbon material obtained by pyrolysis is an amorphous structure, and no peaks of elemental sulfur and pure cotton flowers are observed on the XRD pattern of S-CMTs, indicating that sulfur is fully doped into the carbon structure. FIG. 4 is a view of a sulfur-doped carbon nanotubeFT-IR plot at 1344 and 881cm-1The stretching vibration of the C-S key and the S-S key can be observed at 1167cm-1Stretching vibration of the C — O bond can be observed, further indicating sulfur incorporation into the carbon structure.
(3) Electrochemical performance test
The S-CMTs prepared in the example, Super-P carbon black and sodium carboxymethylcellulose (CMC) are ground and mixed uniformly according to the mass ratio of 70:15:15 by taking water as a solvent, the obtained uniform slurry is coated on a Cu foil and dried in vacuum at 40 ℃ for 12 hours to prepare the Cu foil with the loading capacity of about 1.0mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The solution of propylene carbonate/ethylene fluorocarbonate (volume ratio is 1:0.05) is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as a diaphragm and a counter electrode of the sodium ion battery. The electrochemical performance test employed a CR2032 cell. All the operations related to the cell were carried out in a glove box filled with an argon atmosphere.
The constant current charge and discharge test of the battery is carried out at room temperature, and is carried out in a fixed voltage range of 0.01-3V by using a blue CT2001A multi-channel battery test system. Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were tested using the parsta 4000 electrochemical workstation. CV at 0.1mV s-1The EIS is performed under a sine wave having a frequency in the range of 100kHz to 10mHz and an amplitude of 10.0 mV.
Specific electrochemical properties are shown in FIGS. 5-7. FIG. 5 is a first turn charge/discharge graph of S-CMTs showing first turn charge/discharge capacities of 532 and 850mAh g, respectively-1The coulomb efficiency is about 62.6 percent; the first irreversible capacity loss (37.4%) was due to electrolyte decomposition and formation of a solid electrolyte membrane on the surface of the S-CMTs. FIG. 6 is a graph of the rate capability of S-CMTs at different current densities, showing that S-CMTs are at even high current densities, e.g., at 5 and 10A g-1Its reversible capacity can still be kept 199 and 140mAh g respectively-1. FIG. 7 is a graph of the cycling performance of S-CMTs with a first turn charge capacity of 312mAhg-1And the reversible capacity is 281mAh g after 1000 cycles of circulation-1. The results of FIGS. 5-7 illustrate the sulfur incorporation produced in this exampleThe heterocarbon micron tube has excellent electrochemical performance and can be used as an ideal cathode material of a sodium ion battery.
Comparative example 1
(1) Preparation of CMTs
Weighing 2g of cotton, transferring the cotton into a porcelain boat, transferring the porcelain boat into a tube furnace, heating the porcelain boat to 700 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and then keeping the porcelain boat at 700 ℃ for 3h to obtain black carbon nanotubes (CMTs).
(2) Electrochemical performance test
The CMTs prepared in the example, Super-P carbon black and CMC sodium are ground and mixed uniformly according to the mass ratio of 70:15:15 by using water as a solvent, the obtained uniform slurry is coated on a Cu foil and dried in vacuum at 40 ℃ for 12 hours to prepare the load of about 1.0mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The solution of propylene carbonate/ethylene fluorocarbonate (volume ratio is 1:0.05) is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as a diaphragm and a counter electrode of the sodium ion battery. The electrochemical performance was tested using a CR2032 cell. All the operations related to the cell were carried out in a glove box filled with an argon atmosphere.
The CMTs were tested for sodium ion battery performance using the same procedure and conditions as in example 1, and the results are shown in FIGS. 5-7. As shown in FIGS. 5-7, the first-pass charge/discharge plots (FIG. 5) show that the first-pass charge/discharge capacity of the CMTs is 146/270mAh g-1The cycle performance chart (FIG. 7) shows that the charge/discharge capacity after 1000 cycles of cycle is reduced to 59.6/59.7mAh g-1Significantly lower than the cycling performance of S-CMTs.
Comparative example 1 illustrates that the carbon nanotubes not containing sulfur doping have significantly inferior electrochemical properties to the sulfur-doped carbon nanotubes prepared in example 1 of the present invention.
Example 2
Weigh 1g of cotton into a porcelain boat and transfer to a tube furnace in H2In an S/Ar atmosphere, H2The volume percentage of S is 5 percent, the temperature is raised to 700 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 3 hours, thus obtaining black S-CMTs-2.
The structural characterization and electrochemical performance test of the prepared S-CMTs-2 composite were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 3
2g of cotton are weighed into a porcelain boat and transferred into a tube furnace in H2In an S/Ar atmosphere, H2The volume percentage of S is 10 percent, the temperature is increased to 800 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 3 hours, thus obtaining black S-CMTs-3.
The structural characterization and electrochemical performance test of the prepared S-CMTs-3 composite were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 4
2g of cotton are weighed into a porcelain boat and transferred into a tube furnace in H2In an S/Ar atmosphere, H2The volume percentage of S is 8 percent, the temperature is increased to 600 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 2h, thus obtaining black S-CMTs-4.
The structural characterization and electrochemical performance test of the prepared S-CMTs-4 composite were performed in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 5
2g of cotton are weighed into a porcelain boat and transferred into a tube furnace in H2In an S/Ar atmosphere, H2The volume percentage of S is 6 percent, the temperature is increased to 750 ℃ at the temperature rising rate of 8 ℃/min, and the temperature is kept for 2h, so that black S-CMTs-5 is obtained.
The structural characterization and electrochemical performance test of the prepared S-CMTs-5 composite were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Claims (7)
1. The preparation method of the sulfur-doped carbon micron tube is characterized by comprising the following steps of: direct cotton grafting in H by one-step reaction2Simultaneously carbonizing and vulcanizing in an S/Ar atmosphere to obtain a sulfur-doped carbon micron tube; said H2In an S/Ar atmosphere, H2The volume percentage of S gas is 5-10%; and the step of carbonization and vulcanization is to place the cotton in a tube furnace, heat the cotton to 600-800 ℃ at the speed of 2-10 ℃/min, and then keep the temperature for 2-3 h.
2. The method for preparing the sulfur-doped carbon nanotube as claimed in claim 1, wherein the sulfur doping is more uniform by doping hydrogen sulfide gas at a high temperature of 600-800 ℃.
3. The method of claim 1, wherein the cotton is natural cotton and can be used without any purification treatment.
4. The method of claim 1, wherein the amount of cotton is 1-2 g.
5. A sulfur-doped carbon nanotube prepared by the method of any one of claims 1 to 4.
6. The sulfur-doped carbon nanotube as claimed in claim 5, wherein the surface of the carbon nanotube is doped with sulfur to form a plurality of nanopores with a specific surface area of 307.6m2g-1And the nano holes are micropores.
7. An application of the sulfur-doped carbon micro-tube prepared by the method of any one of claims 1 to 4 as a negative electrode material of a sodium ion battery.
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